CN114879298B - Polarizer and image display device - Google Patents

Polarizer and image display device Download PDF

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Publication number
CN114879298B
CN114879298B CN202210659090.XA CN202210659090A CN114879298B CN 114879298 B CN114879298 B CN 114879298B CN 202210659090 A CN202210659090 A CN 202210659090A CN 114879298 B CN114879298 B CN 114879298B
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group
dichroic substance
polarizer
dichroic
maximum absorption
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CN114879298A (en
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星野渉
高田佳明
藤木优壮
斋藤健吾
石绵靖宏
加藤隆志
后泻敬介
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Fujifilm Corp
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    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133528—Polarisers
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3016—Polarising elements involving passive liquid crystal elements
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/0403—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit the structure containing one or more specific, optionally substituted ring or ring systems
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/08—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of polarising materials
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133528—Polarisers
    • G02F1/133533—Colour selective polarisers
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/50—OLEDs integrated with light modulating elements, e.g. with electrochromic elements, photochromic elements or liquid crystal elements
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K2019/0444—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2323/00—Functional layers of liquid crystal optical display excluding electroactive liquid crystal layer characterised by chemical composition
    • C09K2323/03—Viewing layer characterised by chemical composition
    • C09K2323/031—Polarizer or dye
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/8791—Arrangements for improving contrast, e.g. preventing reflection of ambient light

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Nonlinear Science (AREA)
  • Mathematical Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Theoretical Computer Science (AREA)
  • Polarising Elements (AREA)
  • Liquid Crystal (AREA)
  • Devices For Indicating Variable Information By Combining Individual Elements (AREA)
  • Electroluminescent Light Sources (AREA)
  • Optical Filters (AREA)

Abstract

The application provides a polarizer with high orientation degree and an image display device with the polarizer. The polarizer of the present application is formed from a composition for forming a polarizer, which contains a liquid crystalline compound, a 1 st dichroic substance, and a 2 nd dichroic substance, and has an arrangement structure formed from the 1 st dichroic substance and the 2 nd dichroic substance.

Description

Polarizer and image display device
The application relates to a divisional application of Chinese patent application No.201980022056.8 (International application No. PCT/JP2019/013156, entitled polarizer and image display device) filed on 25 th month 9 of 2020.
Technical Field
The present application relates to a polarizer and an image display device.
Background
Conventionally, when an attenuation function, a polarization function, a scattering function, a light shielding function, or the like of irradiation light including laser light or natural light is required, a device that operates according to different principles for each function is used. Therefore, products corresponding to the above functions are also products manufactured according to different manufacturing processes for the respective functions.
For example, in an image display device (e.g., a liquid crystal display device), a linear polarizer or a circular polarizer is used to control optical rotation or birefringence in display. Also, a circular polarizer is used for an organic light emitting diode (Organic Light Emitting Diode) (organic light emitting diode): OLED) to prevent reflection of external light.
Conventionally, iodine has been widely used as a dichroic material in these polarizers, but a polarizer using an organic dye instead of iodine as a dichroic material has also been studied.
For example, patent document 1 discloses a composition for forming a polarizer, which contains a polymer liquid crystalline compound and a dichroic material.
Technical literature of the prior art
Patent literature
Patent document 1: international publication No. 2017/154907
Disclosure of Invention
Technical problem to be solved by the invention
In this case, the present inventors made reference to the example of patent document 1 to produce a polarizer, and as a result of evaluating the degree of orientation, it is clear that further improvement in the degree of orientation is expected in view of future expected performance improvement of an image display device or the like.
In view of the above-described circumstances, an object of the present invention is to provide a polarizer having a high degree of orientation and an image display device having the polarizer.
Means for solving the technical problems
As a result of intensive studies on the above problems, the present inventors have found that when a polarizer formed from a composition for forming a polarizer containing a liquid crystalline compound, a 1 st dichroic substance and a 2 nd dichroic substance has an alignment structure formed from the 1 st dichroic substance and the 2 nd dichroic substance, the degree of orientation is improved, and have achieved the present invention.
That is, the present inventors have found that the above problems can be solved by the following configuration.
[1] A polarizer comprising a composition for forming a polarizer, which contains a liquid crystalline compound, a 1 st dichroic substance, and a 2 nd dichroic substance, wherein the polarizer has an arrangement structure formed by the 1 st dichroic substance and the 2 nd dichroic substance.
[2] The polarizer according to [1], wherein,
in the arrangement structure, an association is formed between the 1 st dichroic material and the 2 nd dichroic material.
[3] The polarizer according to [1] or [2], wherein,
the absolute value of the difference between the maximum absorption wavelength lambda 2 and the maximum absorption wavelength lambda is greater than 2nm,
the maximum absorption wavelength λ2 is the maximum absorption wavelength in the absorption spectrum of a film formed from a composition containing the 2 nd dichroic substance and the liquid crystalline compound without containing the 1 st dichroic substance,
the maximum absorption wavelength λ is the maximum absorption wavelength in the difference spectrum between the absorption spectrum of the polarizer and the absorption spectrum of a film formed of a composition containing the 1 st dichroic substance and the liquid crystalline compound without the 2 nd dichroic substance.
[4] The polarizer according to any one of [1] or [3], wherein,
The absolute value of the difference between the maximum absorption wavelength lambda 4 and the maximum absorption wavelength lambda 1 is greater than 2nm,
the maximum absorption wavelength λ4 is the maximum absorption wavelength in the absorption spectrum of a film formed from a composition containing the 1 st dichroic substance and the liquid crystalline compound without containing the 2 nd dichroic substance,
the maximum absorption wavelength λ1 is the maximum absorption wavelength in the absorption spectrum of the polarizer.
[5] The polarizer according to any one of [1] or [4], wherein,
in the arrangement structure, the 1 st dichroic material and the 2 nd dichroic material have a crystal structure.
[6] The polarizer according to any one of [1] or [5], wherein,
the intensity of the peak O1 is different from the intensity of the peak O2,
the peak O1 is a peak derived from the periodic structure of the 2 nd dichroic material in the X-ray diffraction spectrum of the polarizer,
the peak O2 is a peak derived from the periodic structure of the 2 nd dichroic material in an X-ray diffraction spectrum of a film formed from a composition containing the 2 nd dichroic material and the liquid crystalline compound without containing the 1 st dichroic material.
[7] The polarizer according to [6], wherein,
the ratio of the intensity of the peak O1 to the intensity of the peak O2 is less than 1.
[8] The polarizer according to any one of [1] or [7], wherein,
in the case of measuring the X-ray diffraction spectrum of the polarizer,
the peak OM of the periodic structure derived from the 1 st dichroic material and the 2 nd dichroic material is detected at a diffraction angle different from a diffraction angle of a peak M2 of the periodic structure derived from the 1 st dichroic material in an X-ray diffraction spectrum for detecting a film formed of a composition containing no 2 nd dichroic material and the 1 st dichroic material and the liquid crystal compound, and a diffraction angle of a peak O2 of the periodic structure derived from the 2 nd dichroic material in an X-ray diffraction spectrum for detecting a film formed of a composition containing no 1 st dichroic material and the 2 nd dichroic material and the liquid crystal compound.
[9] The polarizer according to any one of [1] or [8], wherein,
the stabilized energy which indicates the energy loss when one of the 1 st dichroic material and the 2 nd dichroic material is introduced into the other dichroic material in a structure in which the other dichroic material is arranged alone is less than 72kcal/mol.
[10] The polarizer according to [9], wherein,
the stabilization energy is 55kcal/mol or less.
[11] The polarizer according to [9] or [10], wherein,
the stabilization energy is not more than 35 kcal/mol.
[12] The polarizer according to any one of [1] or [11], wherein,
the 1 st dichroic material is a dichroic material having a maximum absorption wavelength in a range of 560nm or more and 700nm or less,
the 2 nd dichroic material is a dichroic material having a maximum absorption wavelength in a range of 455nm or more and less than 560 nm.
[13] The polarizer according to any one of [1] or [12], wherein,
the absolute value of the difference between the log P value of the side chain of the 1 st dichroic material and the log P value of the side chain of the 2 nd dichroic material is 2.30 or less.
[14] The polarizer of any one of [1] or [13], further comprising a 3 rd dichroic substance having a maximum absorption wavelength in a range of 380nm or more and less than 455 nm.
[15] An image display device having the polarizer described in any one of (1) to (13) above.
Effects of the invention
As described below, according to the present invention, a polarizer having a high degree of orientation and an image display device having the polarizer can be provided.
Drawings
Fig. 1 is a conceptual diagram showing an example of a state in which the 1 st dichroic material and the 2 nd dichroic material are formed into an aligned structure.
Fig. 2 is a conceptual diagram showing an example of the arrangement structure of the 1 st dichroic material and the 2 nd dichroic material.
Fig. 3 is a view schematically showing an example of an absorption spectrum of the polarizer of the present invention.
FIG. 4 is a graph showing XRD (X-ray diffraction) spectra corresponding to films 1-2.
FIG. 5 is a graph showing XRD spectra corresponding to films 1-3.
Fig. 6 is a graph showing an XRD spectrum corresponding to the polarizer (film 1) of example 1.
FIG. 7 is a graph showing XRD spectra corresponding to films 2-4.
FIG. 8 is a graph showing XRD spectra corresponding to film 2-2.
FIG. 9 is a graph showing XRD spectra corresponding to films 2-3.
Fig. 10 is a graph showing an XRD spectrum corresponding to the polarizer (film 2) of example 2.
Detailed Description
The present invention will be described in detail below.
The explanation of the constituent elements described below is sometimes completed according to the representative embodiment of the present invention, but the present invention is not limited to this embodiment.
In the present specification, a numerical range indicated by "to" is a range including numerical values described before and after "to" as a lower limit value and an upper limit value.
Further, each component may be used alone or in combination of two or more. In the case where two or more of the components are used in combination, the content of the components means the total content unless otherwise specified.
The "(meth) acrylate" is a term representing "acrylate" or "methacrylate", the "(meth) acrylic acid" is a term representing "acrylic acid" or "methacrylic acid", and the "(meth) acryl" is a term representing "acryl" or "methacryl".
[ polarizer ]
The polarizer of the present invention is formed from a composition for forming a polarizer, which contains a liquid crystalline compound, a 1 st dichroic substance, and a 2 nd dichroic substance, and has an arrangement structure formed from the 1 st dichroic substance and the 2 nd dichroic substance.
The present inventors have found that when a polarizer having a 1 st dichroic substance and a 2 nd dichroic substance is manufactured, the degree of orientation sometimes becomes high. As a result of examining the details of the reason, it was found that the positional relationship between the 1 st dichroic material and the 2 nd dichroic material in the polarizer is closely related, and that the degree of alignment increases when the 1 st dichroic material and the 2 nd dichroic material form an aligned structure.
In the present invention, the arrangement structure formed by the 1 st dichroic substance and the 2 nd dichroic substance means a state in which one or more molecules of the 1 st dichroic substance and one or more molecules of the 2 nd dichroic substance are aggregated to form an aggregate in the polarizer, and the molecules of the plurality of dichroic substances are periodically arranged in the aggregate.
Fig. 1 is a conceptual diagram showing an example of a state in which the 1 st dichroic material and the 2 nd dichroic material are formed into an aligned structure. The polarizer P has a molecule M of the 1 st dichroic substance, a molecule O of the 2 nd dichroic substance, and a molecule L of the liquid crystalline compound. As shown in fig. 1, an aggregate G including a molecule M and a molecule O is formed, and in the aggregate G, the long axis directions of the molecule M and the molecule O are aligned in the same direction, and the molecule M and the molecule O are arranged so as to be staggered with a period of width w.
The arrangement structure of the 1 st dichroic material and the 2 nd dichroic material is not limited to the arrangement structure of fig. 1, and for example, as shown in fig. 2, the molecules M and O may be arranged to be shifted by the period of the angle a.
In addition, in the polarizer, the 1 st dichroic substance may be polymerized. Likewise, in a polarizer, the 2 nd dichroic substance may polymerize.
[ composition for Forming polarizer ]
The composition for forming a polarizer (hereinafter, also referred to as "the composition") used for forming a polarizer of the present invention contains a liquid crystalline compound, a 1 st dichroic material, and a 2 nd dichroic material. The composition may contain a 3 rd dichroic material, a solvent, a polymerization initiator, an interface modifier, or other components as needed.
The components will be described below.
< liquid Crystal Compound >
The composition contains a liquid crystalline compound. By containing the liquid crystalline compound, the dichroic material can be aligned with a high degree of alignment while suppressing precipitation of the dichroic material.
The liquid crystalline compound is a liquid crystalline compound that does not exhibit dichroism.
As such a liquid crystalline compound, either a low molecular liquid crystalline compound or a high molecular liquid crystalline compound can be used. The "low-molecular liquid crystalline compound" herein refers to a liquid crystalline compound having no repeating unit in its chemical structure. The term "polymer liquid crystalline compound" refers to a liquid crystalline compound having a repeating unit in its chemical structure.
Examples of the low-molecular liquid crystalline compound include liquid crystalline compounds described in JP-A2013-228706.
Examples of the polymer liquid crystalline compound include thermotropic liquid crystalline polymers described in JP 2011-237513A. The polymer liquid crystalline compound may have a crosslinkable group (for example, an acryl group or a methacryl group) at the terminal.
The liquid crystal compound may be used alone or in combination of two or more.
The content of the liquid crystalline compound is preferably 25 to 2000 parts by mass, more preferably 33 to 1000 parts by mass, and even more preferably 50 to 500 parts by mass, relative to 100 parts by mass of the content of the dichroic substance in the composition. Since the content of the liquid crystalline compound is within the above range, the degree of orientation of the polarizer is further improved.
For reasons that the effect of the present invention is more excellent, the liquid crystalline compound is preferably a polymer liquid crystalline compound containing a repeating unit represented by the following formula (1) (hereinafter, also referred to as "repeating unit (1)").
[ chemical formula 1]
In the above formula (1), P1 represents a main chain of a repeating unit, L1 represents a single bond or a 2-valent linking group, SP1 represents a spacer group, M1 represents a mesogenic group, and T1 represents an end group.
Specifically, examples of the main chain of the repeating unit represented by P1 include groups represented by the following formulas (P1-A) to (P1-D), and among them, the group represented by the following formula (P1-A) is preferable from the viewpoints of diversity of monomers as raw materials and easiness of handling.
[ chemical formula 2]
In the formulas (P1-a) to (P1-D), "x" indicates a bonding position to L1 in the formula (1). In the formulae (P1-A) to (P1-D), R 1 、R 2 、R 3 R is R 4 Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms. The alkyl group may be a linear or branched alkyl group, or may be an alkyl group (cycloalkyl group) having a cyclic structure. The number of carbon atoms of the alkyl group is preferably 1 to 5.
The group represented by the formula (P1-A) is preferably one unit of the partial structure of a poly (meth) acrylate obtained by polymerization of a (meth) acrylate.
The group represented by the formula (P1-B) is preferably an ethylene glycol unit formed by ring-opening polymerization of an epoxy group of a compound having an epoxy group.
The group represented by the formula (P1-C) is preferably a propylene glycol unit formed by ring-opening polymerization of an oxetanyl group of a compound having an oxetanyl group.
The group represented by the formula (P1-D) is preferably a siloxane unit of a polysiloxane obtained by polycondensation of a compound having at least one group of an alkoxysilyl group and a silanol group. The compound having at least one group selected from an alkoxysilyl group and a silanol group includes compounds having the formula SiR 4 (OR 5 ) 2 -a compound of the indicated group. Wherein R is 4 And R in (P1-D) 4 Meaning is the same, a plurality of R 5 Each independently represents a hydrogen atom or a carbon atom number1 to 10 alkyl groups.
L1 is a single bond or a 2-valent linking group.
As the 2-valent linking group represented by L1, examples include-C (O) O-, -OC (O) -, -O-, -S-, -C (O) NR 3 -、-NR 3 C(O)-、-SO 2 -and-NR 3 R 4 -and the like. Wherein R is 3 R is R 4 Each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent.
When P1 is a group represented by the formula (P1-A), L1 is preferably a group represented by-C (O) O-for reasons that the effect of the present invention is more excellent.
When P1 is a group represented by the formulae (P1-B) to (P1-D), L1 is preferably a single bond for reasons that the effect of the present invention is more excellent.
The spacer group represented by SP1 preferably includes at least one structure selected from the group consisting of an ethylene oxide structure, a propylene oxide structure, a polysiloxane structure, and a fluorinated alkylene structure, from the viewpoint of easy development of liquid crystallinity, availability of raw materials, and the like.
The ethylene oxide structure represented by SP1 is preferably represented by the formula- (CH) 2 -CH 2 O) n1 -a group represented. Wherein n1 represents an integer of 1 to 20, and represents a bonding position with L1 or M1 in the above formula (1). For reasons that the effect of the present invention is more excellent, n1 is preferably an integer of 2 to 10, more preferably an integer of 2 to 4, and most preferably 3.
Further, for the reason that the effect of the present invention is more excellent, the propylene oxide structure represented by SP1 is preferably represented by (CH) 3 )-CH 2 O) n2 -a group represented. Wherein n2 represents an integer of 1 to 3, and represents a bonding position with L1 or M1.
Further, for the reason that the effect of the present invention is more excellent, the polysiloxane structure represented by SP1 is preferably represented by- (Si (CH) 3 ) 2 -O) n3 -a group represented. Wherein n3 represents an integer of 6 to 10, and represents a bonding position with L1 or M1.
Further, the reason why the effect of the present invention is more excellent is consideredThe fluorinated alkylene structure represented by SP1 is preferably represented by: - (CF) 2 -CF 2 ) n4 -a group represented. Wherein n4 represents an integer of 6 to 10, and represents a bonding position with L1 or M1.
The mesogenic group represented by M1 is a group representing a main skeleton of a liquid crystal molecule contributing to liquid crystal formation. The liquid crystal molecules exhibit liquid crystallinity in an intermediate state (mesophase) of a crystalline state and an isotropic liquid state. The mesogenic group is not particularly limited, and may be referred to, for example, "FlussigeKristalle in Ta bellen II" (VEB DeutscheVerlag fur Grundstoff Industrie, leipzig, 1984), especially, the descriptions on pages 7 to 16, and the descriptions on chapter 3, by the liquid crystal handbook editing Commission, liquid crystal handbooks (Wan, 2000).
The mesogenic group is preferably a group having at least one cyclic structure selected from the group consisting of an aromatic hydrocarbon group, a heterocyclic group, and an alicyclic group.
For the reason that the effect of the present invention is more excellent, the mesogenic group preferably has an aromatic hydrocarbon group, more preferably 2 to 4 aromatic hydrocarbon groups, and still more preferably 3 aromatic hydrocarbon groups.
The mesogenic group is preferably a group represented by the following formula (M1-A) or the following formula (M1-B), more preferably a group represented by the following formula (M1-B), from the viewpoints of the appearance of liquid crystal properties, adjustment of liquid crystal phase transition temperature, availability of raw materials and suitability for synthesis and from the viewpoint of more excellent effects of the present invention.
[ chemical formula 3]
In the formula (M1-A), A1 is a 2-valent group selected from the group consisting of an aromatic hydrocarbon group, a heterocyclic group and an alicyclic group. These groups may be substituted with alkyl groups, fluoroalkyl groups, alkoxy groups, or substituents.
The 2-valent group represented by A1 is preferably a 4-to 6-membered ring. The group having a valence 2 represented by A1 may be a single ring or a condensed ring.
* Represents the bonding position with SP1 or T1.
Examples of the 2-valent aromatic hydrocarbon group represented by A1 include phenylene, naphthylene, fluorene-diyl, anthracene-diyl, and naphthacene-diyl, and from the viewpoints of diversity in mesogenic skeleton design, availability of raw materials, and the like, phenylene or naphthylene is preferable, and phenylene is more preferable.
The heterocyclic group having a valence of 2 represented by A1 may be any of aromatic and non-aromatic, and from the viewpoint of further improving the degree of orientation, it is preferably an aromatic heterocyclic group having a valence of 2.
Examples of the atoms other than carbon constituting the 2-valent aromatic heterocyclic group include nitrogen atom, sulfur atom and oxygen atom. In the case where the aromatic heterocyclic group has a plurality of atoms constituting a ring other than carbon, these atoms may be the same or different.
Specific examples of the 2-valent aromatic heterocyclic group include a pyridylene group (pyridine-diyl group), a pyridazine-diyl group, an imidazole-diyl group, a thiophene group (thiophene-diyl group), a quinoline group (quinoline-diyl group), an isoquinoline group (isoquinoline-diyl group), an oxazole-diyl group, a thiazole-diyl group, an oxadiazole-diyl group, a benzothiazole-diyl group, a benzothiadiazole-diyl group, a phthalimide-diyl group, a thienothiazole-diyl group, a thiazolothiazole-diyl group, a thienothiazole-diyl group, and a thienooxazole-diyl group.
Specific examples of the 2-valent alicyclic group represented by A1 include cyclopentylene and cyclohexylene.
In the formula (M1-A), a1 represents an integer of 1 to 10. When A1 is 2 or more, a plurality of A1 may be the same or different.
In the formula (M1-B), A2 and A3 are each independently A2-valent group selected from the group consisting of an aromatic hydrocarbon group, a heterocyclic group and an alicyclic group. Specific examples and preferred modes of A2 and A3 are the same as those of A1 of the formula (M1-A), and therefore, the description thereof will be omitted.
In the formula (M1-B), A2 represents an integer of 1 to 10, and when A2 is 2 or more, a plurality of A2 s may be the same or different, a plurality of A3 s may be the same or different, and a plurality of LA1 s may be the same or different. For reasons that the effect of the present invention is more excellent, a2 is preferably an integer of 2 or more, and more preferably 2.
In the formula (M1-B), when a2 is 1, LA1 is a 2-valent linking group. When a2 is 2 or more, each of the plurality of LA1 s is independently a single bond or a 2-valent linking group, and at least one of the plurality of LA1 s is a 2-valent linking group. When a2 is 2, one of the two LA1 groups is preferably a 2-valent linking group, and the other is preferably a single bond, for reasons that the effect of the present invention is more excellent.
In the formula (M1-B), examples of the 2-valent linking group represented by LA1 include-O-, - (CH) 2 ) g -、-(CF 2 ) g -、-Si(CH 3 ) 2 -、-(Si(CH 3 ) 2 O) g -、-(OSi(CH 3 ) 2 ) g - (g represents an integer of 1 to 10), -N (Z) -, -C (Z) =c (Z'), -C (Z) =n-, -n=c (Z) -, -C (Z) 2 -C(Z’) 2 -C (O) -, -OC (O) -, -C (O) O-, -O-C (O) O-, -N (Z) C (O) -, -C (O) N (Z) -, -C (Z) =c (Z ') -C (O) O-, -O-C (O) -C (Z) =c (Z') -, C (Z) =n-, -n=c (Z) -, -C (Z) =c (Z ') -C (O) N (Z ") -, -N (Z") -C (O) -C (Z) =c (Z') -, C (Z) =c (Z ') -C (O) -S-, -S-C (O) -C (Z) =c (Z') -, C (Z) =n-n=c (Z ') - (Z, Z', Z "independently represent hydrogen, C1-C4 alkyl, cycloalkyl, aryl, cyano or halogen atom), -C (C) -, -C (N-, -n=s) -, -S (O) -, -O (O) - - (O) S (O) O-, -O (O) S (O) O-, -SC (O) -and-C (O) S-, etc. Among them, from the reason that the effect of the present invention is more excellent, C (O) O-is preferable. LA1 may be a group in which two or more of these groups are combined.
Specific examples of M1 include the following structures. In the following specific examples, "Ac" represents an acetyl group.
[ chemical formula 4]
[ chemical formula 5]
Examples of the terminal group represented by T1 include a hydrogen atom, a halogen atom, a cyano group, a nitro group, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an alkoxycarbonyloxy group having 1 to 10 carbon atoms, an alkoxycarbonyl group (ROC (O) -: R) having 1 to 10 carbon atoms, an acyloxy group having 1 to 10 carbon atoms, an amido group having 1 to 10 carbon atoms, an alkoxycarbonylamino group having 1 to 10 carbon atoms, a sulfonamido group having 1 to 10 carbon atoms, a sulfamoyl group having 1 to 10 carbon atoms, a carbamoyl group having 1 to 10 carbon atoms, a sulfinyl group having 1 to 10 carbon atoms, a ureido group having 1 to 10 carbon atoms, and a (meth) acryloyloxy group. Examples of the (meth) acryloyloxy group-containing group include a group represented by-L-A (L represents a single bond or a linking group), and specific examples of the linking group are the same as those of the above-mentioned L1 and SP 1. A represents a group represented by a (meth) acryloyloxy group.
For the reason that the effect of the present invention is more excellent, T1 is preferably an alkoxy group having 1 to 10 carbon atoms, more preferably an alkoxy group having 1 to 5 carbon atoms, and still more preferably a methoxy group. These terminal groups may be further substituted with these groups or with a polymerizable group described in JP-A2010-244038.
For the reason that the effect of the present invention is more excellent, the number of atoms of the main chain of T1 is preferably 1 to 20, more preferably 1 to 15, still more preferably 1 to 10, and particularly preferably 1 to 7. The number of atoms of the main chain of T1 is 20 or less, whereby the degree of orientation of the polarizer is further improved. Here, the "main chain" in T1 means the longest molecular chain bonded to M1, and hydrogen atoms are not counted in the number of atoms of the main chain of T1. For example, when T1 is n-butyl, the number of atoms of the main chain is 4, and when T1 is sec-butyl, the number of atoms of the main chain is 3.
For reasons that the effect of the present invention is more excellent, the content of the repeating unit (1) is preferably 20 to 100% by mass based on 100% by mass of all the repeating units of the polymer liquid crystalline compound.
In the present invention, the content of each repeating unit contained in the polymer liquid crystalline compound is calculated from the amount (mass) of each monomer to be charged to obtain each repeating unit.
The repeating unit (1) may be contained in the polymer liquid crystalline compound singly or in combination of two or more. Among them, from the viewpoint of the more excellent effect of the present invention, it is preferable that the polymer liquid crystalline compound contains two kinds of repeating units (1).
When the polymer liquid crystalline compound contains two types of repeating units (1), it is preferable that the terminal group represented by T1 in one type (repeating unit a) is an alkoxy group and the terminal group represented by T1 in the other type (repeating unit B) is a group other than an alkoxy group, for the reason that the effect of the present invention is more excellent.
For the reason that the effect of the present invention is more excellent, the terminal group represented by T1 in the repeating unit B is preferably an alkoxycarbonyl group, a cyano group or a (meth) acryloyloxy group-containing group, and more preferably an alkoxycarbonyl group or a cyano group.
For the reason that the effect of the present invention is more excellent, the ratio (A/B) of the content of the repeating unit A in the polymer liquid crystalline compound to the content of the repeating unit B in the polymer liquid crystalline compound is 50/50 to 95/5, more preferably 60/40 to 93/7, still more preferably 70/30 to 90/10.
(weight average molecular weight)
For the reason that the effect of the present invention is more excellent, the weight average molecular weight (Mw) of the polymer liquid crystalline compound is preferably 1000 to 500000, more preferably 2000 to 300000. When the Mw of the polymer liquid crystalline compound is within the above range, the polymer liquid crystalline compound can be easily handled.
In particular, from the viewpoint of suppressing cracks during application, the weight average molecular weight (Mw) of the polymer liquid crystalline compound is preferably 10000 or more, more preferably 10000 to 300000.
From the viewpoint of the temperature range of the degree of alignment, the weight average molecular weight (Mw) of the polymer liquid crystalline compound is preferably less than 10000, more preferably 2000 or more and less than 10000.
The weight average molecular weight and the number average molecular weight in the present invention are values measured by Gel Permeation Chromatography (GPC).
Solvent (eluent): n-methylpyrrolidone
Device name: TOSOH HLC-8220GPC
Tubular column: 3 pieces of TOSOH TSKgelSuperAWM-H (6 mm. Times.15 cm) were used in combination
Column temperature: 25 DEG C
Sample concentration: 0.1 mass%
Flow rate: 0.35ml/min
Calibration curve: the TSK standard polystyrene manufactured by TOSOH uses a calibration curve of 7 samples up to mw=2800000 to 1050 (Mw/mn=1.03 to 1.06)
< 1 st dichromatic substance >
The composition contains a 1 st dichroic substance. The 1 st dichroic material is not particularly limited as long as it can form an arrangement structure with the 2 nd dichroic material, but is preferably a compound having a nucleus of the dichroic material, that is, a color former and a side chain bonded to the end of the color former.
Specific examples of the color former include an aromatic ring group (for example, an aromatic hydrocarbon group, an aromatic heterocyclic group) and an azo group, and a structure having both an aromatic ring group and an azo group is preferable, and a disazo structure having an aromatic heterocyclic group (preferably, a thienothiazole group) and two azo groups is more preferable.
The side chain is not particularly limited, and examples thereof include groups represented by R1, R2, or R3 of the following formula (1).
From the viewpoint of adjusting the color tone of the polarizer, the 1 st dichroic material is preferably a dichroic material having a maximum absorption wavelength in a range of from 560nm to 700nm (more preferably from 560 to 650nm, particularly preferably from 560 to 640 nm).
The maximum absorption wavelength (nm) of the dichroic material in the present specification is determined from the ultraviolet-visible spectrum in the wavelength range of 380 to 800nm measured by a spectrophotometer using a solution in which the dichroic material is dissolved in a good solvent.
The 1 st dichroic substance is preferably a compound represented by formula (1) from the viewpoint of further improving the degree of orientation of the polarizer.
[ chemical formula 6]
In the formula (1), ar1 and Ar2 each independently represent a phenylene group which may have a substituent, a naphthylene group which may have a substituent, and preferably a phenylene group.
In the formula (1), R1 represents a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, an alkoxy group, an alkylthio group, an alkylsulfonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an acyloxy group, an alkylcarbonate group, an alkylamino group, an acylamino group, an alkylcarbonylamino group, an alkoxycarbonylamino group, an alkylsulfonylamino group, an alkylsulfamoyl group, an alkylcarbamoyl group, an alkylsulfinyl group, an alkylureyl group, an alkylphosphoramido group, an alkylimino group or an alkylsilyl group.
The carbon atom of the above alkyl group may be replaced by-O-, -CO-, -C (O) -O-, -O-C (O) -, -Si (CH) 3 ) 2 -O-Si(CH 3 ) 2 -N (R1 '), -CO-N (RI '), -N (R1 '), -C (O) -O-, -O-C (O) -N (R1 '), -N (R1 ') -C (O) -N (R1 '), -ch=ch-, -C tri-C-, -n=n-, -C (R1 ')=ch-C (O) -or-O-C (O) -O-substitution.
In the case where R1 is a group other than a hydrogen atom, the hydrogen atom of each group may be a halogen atom, a nitro group, a cyano group or-N (R1') 2 Amino, -C (R1 ') =c (R1') -NO 2 -C (R1 ') =c (R1 ') -CN or-C (R1 ') =c (CN) 2 And (3) substitution.
R1' represents a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms. In the case where a plurality of R1's are present in each group, they may be the same or different from each other.
In the formula (1), R2 and R3 each independently represent a hydrogen atom, a substituent having 1 to 20 carbon atoms, or a linear or branched alkyl group, alkenyl group, alkoxy group, acyl group, alkoxycarbonyl group, alkylamide group, alkylsulfonyl group, aryl group, arylcarbonyl group, arylsulfonyl group, aryloxycarbonyl group or aralkylamide group.
The carbon atom of the above alkyl group may be represented by-O-, -S-, -C (O) -O-, and-O-C (O) -, -C (O) -S-, -S-C (O) -, -Si (CH) 3 ) 2 -O-Si(CH 3 ) 2 -NR2'-, -NR2' -CO-, -CO-NR2'-, -NR2' -C (O) -O-, -O-C (O) -NR2'-, -NR2' -C (O) -NR2'-, -ch=ch-, -c≡c-, -n=n-, -C (R2')=ch-C (O) -or-O-C (O) -O-substitution.
In the case where R2 and R3 are groups other than hydrogen atoms, the hydrogen atoms of each group may be selected from halogen atoms, nitro groups, cyano groups, -OH groups, -N (R2') 2 Amino, -C (R2 ') =c (R2') -NO 2 、-C(R2’)＝C(R2’)-CN、-C(R2’)＝C(CN) 2 And (3) substitution.
R2' represents a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms. In the case where a plurality of R2's are present in each group, they may be the same as or different from each other.
R2 and R3 may be bonded to each other to form a ring, and R2 or R3 may be bonded to Ar2 to form a ring.
From the viewpoint of light resistance, R1 is preferably an electron withdrawing group, and R2 and R3 are preferably groups having low electron donating properties.
Specific examples of such a group include an alkylsulfonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an acyloxy group, an alkylsulfonylamino group, an alkylsulfamoyl group, an alkylsulfinyl group, and an alkylureyl group, and examples of R2 and R3 include those having the following structures. In the above formula (1), the group having the following structure is represented by a form including a nitrogen atom to which R2 and R3 are bonded.
[ chemical formula 7]
Specific examples of the 1 st dichroic material are shown below, but are not limited thereto.
[ chemical formula 8]
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< 2 nd dichromatic substance >
The composition contains a 2 nd dichroic substance. The 2 nd dichroic substance is a compound different from the 1 st dichroic substance, specifically, a chemical structure thereof.
The 2 nd dichroic material is not particularly limited as long as it can form an arrangement structure with the 1 st dichroic material, but is preferably a compound having a nucleus of the dichroic material, that is, a color former and a side chain bonded to the end of the color former.
Specific examples of the color former include an aromatic ring group (for example, an aromatic hydrocarbon group, an aromatic heterocyclic group) and an azo group, and a structure having both an aromatic hydrocarbon group and an azo group is preferable, and a disazo or trisazo structure having an aromatic hydrocarbon group and two or three azo groups is more preferable.
The side chain is not particularly limited, and examples thereof include groups represented by R4, R5, or R6 of the following formula (2).
From the viewpoint of adjusting the color tone of the polarizer, the 2 nd dichroic material is preferably a dichroic material having a maximum absorption wavelength in a range of 455nm or more and less than 560nm (more preferably 455 to 555nm, particularly preferably 455 to 550 nm).
In particular, when a 1 st dichroic material having a maximum absorption wavelength of 560 to 700nm and a 2 nd dichroic material having a maximum absorption wavelength of 455nm or more and less than 560nm are used, it is easier to adjust the color tone of the polarizer.
The 2 nd dichroic substance is preferably a compound represented by formula (2) from the viewpoint of further improving the degree of orientation of the polarizer.
[ chemical formula 9]
In formula (2), n represents 1 or 2.
In the formula (2), ar3, ar4, and Ar5 each independently represent a phenylene group which may have a substituent, a naphthylene group which may have a substituent, or a heterocyclic group which may have a substituent.
The heterocyclic group may be either aromatic or non-aromatic.
Examples of the atoms other than carbon constituting the aromatic heterocyclic group include nitrogen atom, sulfur atom and oxygen atom. In the case where the aromatic heterocyclic group has a plurality of atoms constituting a ring other than carbon, these atoms may be the same or different.
Specific examples of the aromatic heterocyclic group include a pyridylene group (pyridine-diyl group), a pyridazine-diyl group, an imidazole-diyl group, a thiophene group (thiophene-diyl group), a quinoline group (quinoline-diyl group), an isoquinoline group (isoquinoline-diyl group), an oxazole-diyl group, a thiazole-diyl group, an oxadiazole-diyl group, a benzothiazole-diyl group, a benzothiadiazole-diyl group, a phthalimide-diyl group, a thienothiazole-diyl group, a thiazolothiazole-diyl group, a thienothiothiophene-diyl group, and a thienooxazole-diyl group.
In formula (2), R4 is as defined for R1 in formula (1).
In formula (2), R5 and R6 are as defined for R2 and R3 in formula (1), respectively.
From the viewpoint of light resistance, R4 is preferably an electron withdrawing group, and R5 and R6 are preferably groups having low electron donating properties.
Of such groups, the specific example when R4 is an electron withdrawing group is the same as the specific example when R1 is an electron withdrawing group, and the specific example when R5 and R6 are groups having low electron donating properties is the same as the specific example when R2 and R3 are groups having low electron donating properties.
A specific example of the 2 nd dichroic material is shown below, but is not limited thereto.
[ chemical formula 10]
(difference in logP values)
The absolute value of the difference between the log p value of the side chain of the 1 st dichroic material and the log p value of the side chain of the 2 nd dichroic material (hereinafter, also referred to as "log p difference") is preferably 2.30 or less, more preferably 2.0 or less, further preferably 1.5 or less, and particularly preferably 1.0 or less. When the log p difference is 2.30 or less, the affinity between the 1 st dichroic material and the 2 nd dichroic material is improved, and the alignment structure is more easily formed, so that the degree of alignment of the polarizer is further improved.
In addition, in the case where there are a plurality of side chains of the 1 st dichroic substance or the 2 nd dichroic substance, at least one log p difference preferably satisfies the above-described value.
Here, the side chains of the 1 st dichroic material and the 2 nd dichroic dye are groups bonded to the ends of the color-forming groups. For example, when the 1 st dichroic substance is a compound represented by formula (1), R1, R2, and R3 in formula (1) are side chains, and when the 2 nd dichroic substance is a compound represented by formula (2), R4, R5, and R6 in formula (2) are side chains. In particular, in the case where the 1 st dichroic substance is a compound represented by the formula (1), and the 2 nd dichroic substance is a compound represented by the formula (2), at least one log p difference preferably satisfies the above-described value among a difference between log p values of R1 and R4, a difference between log p values of R1 and R5, a difference between log p values of R2 and R4, and a difference between log p values of R2 and R5.
The log p value is an index indicating the hydrophilicity and hydrophobicity of the chemical structure, and is sometimes referred to as a hydrophilicity/hydrophobicity parameter. The logP values can be calculated using software such as chembio draw ultra or hsppi (ver.4.1.07). Further, it can be experimentally obtained by the method of OECDGuidelinesforthe TestingfChemicals, sections1, testNo.117, or the like. In the present invention, unless otherwise specified, the value calculated by inputting the structural formula of the compound into hsppi (ver.4.1.07) is employed as log p value.
< 3 rd dichromatic substance >
The composition preferably contains a 3 rd dichroic substance. The 3 rd dichroic material is a dichroic material other than the 1 st dichroic material and the 2 nd dichroic material, and specifically, has a chemical structure different from that of the 1 st dichroic material and the 2 nd dichroic material. If the composition contains the 3 rd dichroic substance, there is an advantage in that the color tone of the polarizer can be easily adjusted.
The maximum absorption wavelength of the 3 rd dichroic material is preferably 380nm or more and less than 455nm, more preferably 385 to 454nm.
Specific examples of the 3 rd dichroic material include compounds represented by formula (1) described in international publication No. 2017/195833, other than the 1 st dichroic material and the 2 nd dichroic material.
(content of dichromatic substance)
In the composition, the content of the dichroic material is preferably 0.1 to 99 parts by mass, more preferably 1 to 60 parts by mass, and particularly preferably 1.5 to 30 parts by mass, relative to 100 parts by mass of the total amount of the dichroic material and the liquid crystalline compound.
The content of the 1 st dichroic substance is preferably 40 to 90 parts by mass, more preferably 55 to 85 parts by mass, relative to 100 parts by mass of the content of the dichroic substance in the composition.
The content of the 2 nd dichroic substance is preferably 6 to 50 parts by mass, more preferably 8 to 45 parts by mass, relative to 100 parts by mass of the content of the dichroic substance in the composition.
When the composition contains the 3 rd dichroic substance, the content of the 3 rd dichroic substance is preferably 3 to 30 parts by mass, more preferably 5 to 25 parts by mass, relative to 100 parts by mass of the content of the dichroic substance in the composition.
The content of the dichroic material means the total amount of the 1 st dichroic material and the 2 nd dichroic material, and when the composition contains the 3 rd dichroic material, the content of the 3 rd dichroic material is included in the total amount.
The content ratio of the 1 st dichroic material, the 2 nd dichroic material, and the 3 rd dichroic material used as needed can be arbitrarily set in order to adjust the color tone of the polarizer. However, the content ratio of the 2 nd dichroic material to the 1 st dichroic material (2 nd dichroic material/1 st dichroic material) is preferably 0.1 to 10, more preferably 0.2 to 5, and particularly preferably 0.3 to 0.8 in terms of mole. When the content ratio of the 2 nd dichroic material to the 1 st dichroic material is within the above range, the arrangement structure of the 1 st dichroic material and the 2 nd dichroic material is more easily formed.
< solvent >
From the viewpoint of handleability, the composition preferably contains a solvent.
Examples of the solvent include ketones (e.g., acetone, 2-butanone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone), ethers (e.g., dioxane, tetrahydrofuran, tetrahydropyran, dioxolane, tetrahydrosugar alcohol, and cyclopentylmethyl ether), aliphatic hydrocarbons (e.g., hexane), alicyclic hydrocarbons (e.g., cyclohexane), aromatic hydrocarbons (e.g., benzene, toluene, xylene, and trimethylbenzene), halogenated carbons (e.g., dichloromethane, chloroform, dichloroethane, dichlorobenzene, and chlorotoluene), esters (e.g., methyl acetate, ethyl acetate, butyl acetate, and diethyl carbonate), alcohols (e.g., ethanol, isopropanol, butanol, and cyclohexane), cellosolve (e.g., methylcellosolve, ethylcellosolve, and 1, 2-dimethoxyethane), cellosolve acetate esters, sulfoxides (e.g., dimethyl sulfoxide), amides (e.g., dimethylformamide and dimethylacetamide), N-methylpyrrolidone, N-ethylpyrrolidone, 1, 3-dimethyl-2-imidazolidinone, and heterocyclic compounds (e.g., pyridine), and organic solvents such as water. These solvents may be used singly or in combination of two or more.
Among these solvents, an organic solvent is preferably used, and a halogenated carbon or ketone is more preferably used, for the reason that the effect of the present invention is more excellent.
When the composition contains a solvent, the content of the solvent is preferably 70 to 99.5% by mass, more preferably 80 to 99% by mass, and even more preferably 85 to 98% by mass, based on the total mass of the composition, for the reason that the effect of the present invention is more excellent.
< interfacial modifier >
The composition preferably comprises an interface modifier. By including the interface modifier, smoothness of the coated surface is improved, degree of orientation is improved, or dishing and non-uniformity are controlled, and thus improvement in-plane uniformity can be expected.
The interface modifier is preferably one that aligns a polymer liquid crystal compound horizontally, and the compounds described in paragraphs [0253] to [0293] of JP-A2011-237513 (horizontal alignment agent) can be used. Furthermore, a fluoro (meth) acrylate polymer described in [0018] to [0043] of JP-A-2007-272185 and the like can be used. As the interface modifier, other compounds may be used.
When the composition contains the interface modifier, the content of the interface modifier is preferably 0.001 to 5 parts by mass, and more preferably 0.01 to 3 parts by mass, relative to 100 parts by mass of the total of the liquid crystalline compound and the dichroic material in the composition, for the reason that the effect of the present invention is more excellent.
< polymerization initiator >
The composition of the present invention preferably contains a polymerization initiator for the reason that the effect of the present invention is more excellent.
The polymerization initiator is not particularly limited, but is preferably a photopolymerization initiator which is a compound having photosensitivity.
As the photopolymerization initiator, various compounds can be used without particular limitation. Examples of the photopolymerization initiator include an α -carbonyl compound (U.S. Pat. No. 2367661 and U.S. Pat. No. 2367670), an acyloin ether (U.S. Pat. No. 2448828), an α -hydrocarbon substituted aromatic acyloin compound (U.S. Pat. No. 2722512), a polynuclear quinone compound (U.S. Pat. No. 3046127 and the same specification as No. 2951758), a combination of a triarylimidazole dimer and p-aminophenyl ketone (U.S. Pat. No. 3549367), an acridine and phenazine compound (Japanese patent application laid-open No. 60-105667 and U.S. Pat. No. 4239850), an oxadiazole compound (Japanese patent application laid-open No. 4212970) and an acylphosphine oxide compound (Japanese patent application laid-open No. 63-040799, japanese patent application laid-open No. 5-029234, japanese patent application laid-open No. 10-095788 and Japanese patent application laid-open No. 10-029997).
As such photopolymerization initiators, commercially available products can be used, and examples thereof include Irgacure184, irgacure907, irgacure369, irgacure651, irgacure819, irgacure OXE-01, etc. manufactured by BASF corporation.
When the composition contains a polymerization initiator, the content of the polymerization initiator is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 15 parts by mass, based on 100 parts by mass of the total of the liquid crystalline compound and the dichroic material in the composition, for the reason that the effect of the present invention is more excellent. When the content of the polymerization initiator is 0.01 parts by mass or more, the durability of the polarizer is good, and since it is 30 parts by mass or less, the orientation of the polarizer becomes better.
< substituent >
Substituents in the present specification are described.
Examples of the substituent include an alkyl group (preferably an alkyl group having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms, for example, methyl, ethyl, isopropyl, t-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl and the like), an alkenyl group (preferably an alkenyl group having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, particularly preferably 2 to 8 carbon atoms, for example, vinyl, aryl, 2-butenyl, 3-pentenyl and the like), an alkynyl group
(preferably 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, particularly preferably 2 to 8 carbon atoms, for example, propargyl, 3-pentynyl and the like), aryl (preferably 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, for example, phenyl, 2, 6-diethylphenyl, 3, 5-bistrifluoromethylphenyl, styryl, naphthyl, biphenyl and the like), substituted or unsubstituted amino (preferably 0 to 20 carbon atoms, more preferably 0 to 10 carbon atoms, particularly preferably 0 to 6 carbon atoms, for example, unsubstituted amino, methylamino, dimethylamino, diethylamino, anilino and the like), alkoxy (preferably 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, for example, methoxy, ethoxy, butoxy and the like), oxycarbonyl (preferably 2 to 20 carbon atoms, more preferably 2 to 15 carbon atoms, particularly preferably 2 to 15 carbon atoms, for example, methoxycarbonyl, preferably 2 to 10 carbon atoms, for example, benzoyl, 2 to 10 carbon atoms, more preferably 2 to 10 carbon atoms, phenylcarbonyl, particularly preferably 2 to 20 carbon atoms, acetyl, 2 to 10 carbon atoms, for example, acetyl, 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, for example, acetyl, 2 to 20 carbon atoms, etc.), benzoyl, phenylcarbonyl, more preferably 2 to 10 carbon atoms, acetyl, phenylcarbonyl, 2 to 10 carbon atoms, etc, particularly preferably 2 to 6 in carbon number, for example, methoxycarbonylamino group and the like, aryloxycarbonylamino group (preferably 7 to 20 in carbon number, more preferably 7 to 16 in carbon number, particularly preferably 7 to 12 in carbon number, for example, phenoxycarbonylamino group and the like), sulfonylamino group (preferably 1 to 20 in carbon number, more preferably 1 to 10 in carbon number, particularly preferably 1 to 6 in carbon number, for example, methanesulfonylamino group, benzenesulfonylamino group and the like), sulfamoyl group (preferably 0 to 20 in carbon number, more preferably 0 to 10 in carbon number, particularly preferably 0 to 6 in carbon number, for example, sulfamoyl group, methylsulfamoyl group, dimethylsulfamoyl group, phenylsulfamoyl group and the like), carbamoyl group (preferably 1 to 20 in carbon number, more preferably 1 to 10 in carbon number, particularly preferably 1 to 6 in carbon number, for example, unsubstituted carbamoyl group, methylcarbamoyl group, diethylcarbamoyl group, phenylsulfamoyl group and the like), benzylthio group (preferably 1 to 20 in carbon number, particularly preferably 1 to 20 in number, 10 in the like), phenylthio group (preferably 1 to 20 in carbon number, particularly preferably 1 to 20 in carbon number, 6 in the like), phenylthio group and the like, particularly preferably 1 to 20 in the number, carbon number, 10 in the phenylthio group, particularly preferably 1 to 10 in the phenylthio group, and the like, particularly preferably 1 to 10 in the number, more preferably 1 to 10 carbon atoms, particularly preferably 1 to 6 carbon atoms, for example, a methanesulfonyl group, a benzenesulfonyl group, etc.), a ureido group (preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, particularly preferably 1 to 6 carbon atoms, for example, an unsubstituted ureido group, methylureido group, phenylureido group, etc.), a phosphoric acid amide group (preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, particularly preferably 1 to 6 carbon atoms, for example, a diethylphosphoric acid amide group, a benzylphosphoric acid amide group, etc.), a hydroxyl group, a mercapto group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), a cyano group, a nitro group, a hydroxamic acid group, a sulfinyl group, a hydrazino group, an imino group, an azo group, a heterocyclic group (preferably 1 to 30 carbon atoms, more preferably a heterocyclic group having 1 to 12 carbon atoms), examples of the heterocyclic group include a hetero atom such as a nitrogen atom, an oxygen atom, and a sulfur atom, and examples thereof include an epoxy group, an oxetanyl group, an imidazolyl group, a pyridyl group, a quinolyl group, a furyl group, a piperidyl group, a morpholino group, a maleimide group, a benzoxazolyl group, a benzimidazolyl group, and a benzothiazole group, a silyl group (preferably a silyl group having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, and particularly preferably 3 to 24 carbon atoms, and examples thereof include a trimethylsilyl group, a triphenylsilyl group, and the like), a carboxyl group, a sulfonic acid group, and a phosphoric acid group, and the like.
[ Association in polarizer ]
In the arrangement structure formed of the 1 st dichroic substance and the 2 nd dichroic substance in the present invention, the 1 st dichroic substance and the 2 nd dichroic substance are preferably formed with an association body. If the association is formed, there are advantages in that the degree of orientation and light resistance of the polarizer are further improved, and the color tone of the polarizer is easily adjusted.
As a verification method of the formation of an association between the 1 st dichroic material and the 2 nd dichroic material, a method based on the maximum absorption wavelength measured using a film formed as follows can be given.
In addition, when each film (polarizer) is manufactured, the kind of the dichroic material included in each film is changed, and the kind of the lower layer (for example, substrate), the concentration of the composition, and the coating conditions are provided, and attention is paid to equalize the area and film thickness of the film.
Specifically, the composition (composition containing at least the 1 st dichroic substance, the 2 nd dichroic substance, and the liquid crystalline compound) is cast on a substrate (for example, green sheet glass), and the composition is heated on a hot plate until it becomes a liquid crystal state, and cooled to room temperature to form a film 1 (corresponding to the polarizer of the present invention). Then, the absorption spectrum of the film 1 was measured at 1nm intervals in the wavelength range of 380 to 800 nm. The film 1 was heated again at 10℃and the absorption spectrum was measured to determine the maximum absorption wavelength λ1.
Then, a composition 4 (a composition containing at least a liquid crystal compound and a 1 st dichroic substance, without containing a 2 nd dichroic substance) containing the same components as the composition except for not containing the 2 nd dichroic substance was prepared. Then, the absorption spectra of films 1 to 4 formed using composition 4 were obtained in the same manner as the absorption spectra of film 1 (polarizer of the present invention) was measured.
Then, the absorption spectrum of the film 1-4 is subtracted from the absorption spectrum of the film 1 to obtain a difference spectrum, and the maximum absorption wavelength λ of the obtained difference spectrum is obtained.
Next, a composition 2 (a composition containing at least a liquid crystal compound and a 2 nd dichroic substance, without containing a 1 st dichroic substance) having the same composition as the composition except that the 1 st dichroic substance was not contained was prepared. Then, the maximum absorption wavelength λ2 of the film 1-2 formed using the composition 2 was determined in the same manner as the maximum absorption wavelength λ1 of the film 1 (polarizer of the present invention) was measured.
Fig. 3 is a diagram schematically showing the absorption spectra of the respective films produced as described above. As shown in fig. 3, in the polarizer of the present invention, it is preferable that the maximum absorption wavelength λ is different from the maximum absorption wavelength λ2. In the present invention, "the maximum absorption wavelength λ is different from the maximum absorption wavelength λ2" means that the absolute value of the difference between the maximum absorption wavelength λ and the maximum absorption wavelength λ2 is larger than 2nm. The absolute value of the difference between the maximum absorption wavelength λ and the maximum absorption wavelength λ2 is preferably 5nm or more, and more preferably 10nm or more. The upper limit value of the absolute value of the difference between the maximum absorption wavelength λ and the maximum absorption wavelength λ2 is preferably 100nm or less.
In this way, when the maximum absorption wavelength λ is different from the maximum absorption wavelength λ2, it can be said that the 1 st dichroic substance associates with the 2 nd dichroic substance. The reason for this will be explained below.
The difference in composition between film 1 and films 1-4 is the presence or absence of the 2 nd dichroic substance. Therefore, it can be predicted that the absorption spectrum of the film 1 approximately coincides with the difference spectrum of the absorption spectra of the films 1 to 4 and the absorption spectrum derived from the 2 nd dichroic substance. Thus, in the case where the maximum absorption wavelength λ of the difference spectrum and the maximum absorption wavelength λ2 of the absorption spectrum of the film 2 (containing the 2 nd dichroic substance but not the 1 st dichroic substance) agree, it can be said that the 2 nd dichroic substance is not absorbed by the 1 st dichroic substance but exists in the film (polarizer).
On the other hand, as shown in fig. 3, the difference between the maximum absorption wavelength λ and the maximum absorption wavelength λ2 means a state in which the absorption spectrum derived from the 2 nd dichroic material is hardly detected from the difference spectrum. That is, it is considered that the 1 st dichroic substance associates with the 2 nd dichroic substance in the film 1 (for example, a phenomenon that one dichroic substance is absorbed by another dichroic substance or the like occurs), and the absorption spectrum of the 2 nd dichroic substance is not detected from the difference spectrum. In this case, the waveform of the absorption spectrum of the film 1 is different from that of the film 2.
As shown in fig. 3, in the polarizer of the present invention, it is preferable that the maximum absorption wavelength λ1 is different from the maximum absorption wavelength λ4. In the present invention, "the maximum absorption wavelength λ1 is different from the maximum absorption wavelength λ4" means that the absolute value of the difference between the maximum absorption wavelength λ1 and the maximum absorption wavelength λ4 is larger than 2nm. The absolute value of the difference between the maximum absorption wavelength λ1 and the maximum absorption wavelength λ4 is preferably 5nm or more, and more preferably 7nm or more. The upper limit value of the absolute value of the difference between the maximum absorption wavelength λ1 and the maximum absorption wavelength λ4 is preferably 40nm or less.
In particular, in the case where the maximum absorption wavelength of the 1 st dichroic material is larger than the maximum absorption wavelength of the 2 nd dichroic material, it is preferable that the maximum absorption wavelength λ1 is smaller than the maximum absorption wavelength λ4. That is, the value obtained by subtracting λ1 from λ4 (λ4- λ1) is preferably more than 2nm, more preferably 5nm or more. The upper limit of the value obtained by subtracting λ1 from λ4 is preferably 40nm or less.
In this way, when the maximum absorption wavelength λ1 is different from the maximum absorption wavelength λ4, it can be said that the 1 st dichroic substance associates with the 2 nd dichroic substance. The reason for this will be explained below.
The difference in composition between film 1 and films 1-4 is the presence or absence of the 2 nd dichroic substance. In the case where the maximum absorption wavelength of the 1 st dichroic substance is larger than the maximum absorption wavelength of the 2 nd dichroic substance, since the maximum absorption wavelength of the 1 st dichroic substance is detected, it can be predicted that the maximum absorption wavelength λ1 of the film 1 coincides with the maximum absorption wavelength λ4 of the films 1 to 4. Thus, when the maximum absorption wavelength λ1 coincides with the maximum absorption wavelength λ4, it can be said that the 1 st dichroic substance is not absorbed by the 2 nd dichroic substance but exists in the film (polarizer).
In contrast, as shown in fig. 3, a maximum absorption wavelength λ1 being smaller than a maximum absorption wavelength λ4 means that the absorption spectrum derived from the 1 st dichroic substance is in a weakened state. That is, it is considered that the 1 st dichroic substance associates with the 2 nd dichroic substance in the film 1 (for example, a phenomenon such that one dichroic substance is absorbed by the other dichroic substance occurs), and the maximum absorption wavelength shifts to the side of the 2 nd dichroic substance where the maximum absorption wavelength, that is, the wavelength is small.
[ Crystal Structure in polarizer ]
In the arrangement structure formed of the 1 st dichroic substance and the 2 nd dichroic substance in the present invention, the 1 st dichroic substance and the 2 nd dichroic substance are preferably formed with a crystal structure. If the crystal structure is formed, there are advantages in that the degree of orientation and light resistance of the polarizer are further improved, and the color tone of the polarizer is easily adjusted.
In addition, the 1 st dichroic substance and the 2 nd dichroic substance may form a crystal structure simultaneously with the formation of the association body.
As a method for verifying that the 1 st dichroic material and the 2 nd dichroic material have a crystal structure, for example, a method using an X-ray diffraction (XRD) method is given.
When a crystal structure is formed in the dichroic material, a peak corresponding to the crystal structure is observed by X-ray diffraction. In the polarizer of the present invention, in addition to the crystal structures based on the 1 st dichroic substance and the 2 nd dichroic substance, the crystal structures based on the 1 st dichroic substance and the crystal structures based on the 2 nd dichroic substance can be observed. These crystallinity are observed based on the intensity of the X-ray peaks derived from the respective crystal structures.
Specifically, when considering that the 1 st dichroic material and the 2 nd dichroic material are contained and crystal structures based on the 1 st dichroic material and the 2 nd dichroic material are formed, it is considered that there is a peak intensity (referred to as P OM ) Peak intensity derived from crystal structure based on the 1 st dichromatic substance (referred to as P M ) And peak intensities derived from crystal structures based on the 2 nd dichroic substance (referred to as PO).
Also, the peak intensity (referred to as P) of the crystal structure derived from the 1 st dichroic substance when the 1 st dichroic substance is contained but the 2 nd dichroic substance is not contained can be considered M1 ) Peak intensity (referred to as P) of crystal structure derived from the 2 nd dichroic substance when the 2 nd dichroic substance is contained but the 1 st dichroic substance is not contained O1 )。
In the case where the 1 st dichroic substance and the 2 nd dichroic substance form a crystal structure, P M And P M1 Different, P O And P O1 Different. At P M Less than P M1 And P is O Less than P O1 P in the case of (1) M Peak and P O The peak may not be detected, at p M Greater than P M1 And P O Greater than P O1 P in the case of (1) M1 Peak and P O1 The peak may not be detected. For example, at P O Relative to P O1 In the case of small size, it is considered that this means a decrease in crystallinity of the crystal structure derived from the 2 nd dichroic substance Low (size of crystal structure or number of crystal structures reduced).
As a method for verifying the formation of the crystal structures of the 1 st dichroic material and the 2 nd dichroic material, an example of a method using an X-ray diffraction (XRD) method will be described in more detail below. First, film 1 (polarizer of the present invention) and film 1-2 used for measurement of the maximum absorption wavelength were prepared.
Then, a composition 3 (a composition containing at least a liquid crystalline compound without containing the 1 st dichroic substance and the 2 nd dichroic substance) containing the same components as the composition except for not containing the 1 st dichroic substance and the 2 nd dichroic substance was prepared. Films 1 to 3 were obtained in the same manner as in the production method of film 1 (polarizer of the present invention) except that the prepared composition 3 was used.
Then, the films 1 (polarizer of the present invention), 1-2 and 3 were subjected to X-ray diffraction measurement using an X-ray diffraction apparatus for film evaluation (manufactured by Rigaku Corporation, trade name: smartLab in-plane optical system). Hereinafter, the X-ray diffraction analysis performed using the in-plane method is also referred to as "in-plane XRD". In-plane XRD was performed by irradiating X-rays onto the surface of the polarizer using a thin film X-ray diffraction apparatus under the following conditions. The direction in which the liquid crystal and the dichroic material are aligned in the long axis direction is defined as the azimuth angle And in-plane XRD in all directions is performed in 15 DEG units by +.>Scanning to determine the direction in the plane of the substrate where the peak intensity is greatest. The XRD spectrum described later was compared using the spectrum measured in the in-plane direction. The peak intensity was normalized to a film thickness corresponding to an X-ray incidence length at an X-ray incidence angle of 0.2 °.
Since the films 1, 1-2 and 1-3 contain a liquid crystalline compound, a peak having a half-width of less than 2 ° (peak a) and a peak having a half-width of 2 ° (halo) (peak B) were observed in the XRD spectrum measured as described above.
For reasons that the effect of the present invention is more excellent, the diffraction angle of the peak a is preferably less than 17 °.
Further, the diffraction angle of the peak B is preferably 17 ° or more from the viewpoint of the more excellent effect of the present invention.
When XRD spectra of the film 1, the film 1-2, the film 1-3, and the film 1-4 are compared, it is judged that the 1 st dichroic substance and the 2 nd dichroic substance form crystal structures when the following condition (i) or (ii) is satisfied. In contrast, when any one of the following conditions (i) and (ii) is not satisfied, it is determined that the 1 st dichroic material and the 2 nd dichroic material have no crystal structure.
Condition (i): among the peaks a of the films 1-2, a peak of a diffraction angle not observed in the XRD spectrum of the film 1-3 (also referred to as a peak O2) is not observed in the XRD spectrum of the film 1, or is larger than a peak intensity of a peak having the same diffraction angle as the peak O2 (also referred to as a peak O1) even in the case of being observed in the XRD spectrum of the film 1. That is, the ratio of the intensity of the peak O1 to the intensity of the peak O2 is less than 1.
Condition (ii): among the peaks A of film 1, the peaks of diffraction angles not observed in the XRD spectra of films 1-3 (also referred to as peaks OM) were also not observed in the XRD spectra of films 1-2 and 1-4. That is, in the case where a peak of the diffraction angle not observed in the XRD spectrum of the film 1-3 is defined as a peak O2 in the peak A of the film 1-2, and a peak of the diffraction angle not observed in the XRD spectrum of the film 1-3 is defined as a peak M2 in the peak A of the film 1-4, the positions of the diffraction angles of the detected peaks O2 and M2 are different from the positions of the detected diffraction angle of the detected peak O M.
In addition, as described above, since the conditions for producing the films 1, 1-2, 1-3 and 1-4 and the measurement conditions for XRD are matched, peaks of XRD spectra can be compared.
First, a reason why it can be determined that the 1 st dichroic material and the 2 nd dichroic material have a crystal structure by satisfying the condition (i) will be described.
The peak O2 is a peak corresponding to the 2 nd dichroic substance. Therefore, it is considered that the peak O2 (peak O1) is also generally detected for the film 1 (polarizer of the present invention) containing the 2 nd dichroic substance.
On the other hand, it is assumed that the phenomenon that the peak O1 is not detected or the intensity of the peak O1 is small is caused by the following reason, although the polarizer contains the 2 nd dichroic material: in the polarizer, the 2 nd dichroic substance and the 1 st dichroic substance have some interaction, so that the 1 st dichroic substance and the 2 nd dichroic substance are formed with a periodically arranged structure (more specifically, a crystal structure).
The condition (i) is specifically described using XRD spectrum. The details of the composition used for forming each film are described in detail in the following explanation of XRD spectrum of example 1.
Fig. 4 shows XRD spectra of films 1-2 using a polymer liquid crystalline compound L1 described later as a liquid crystalline compound and a 2 nd dichroic substance O1 as a 2 nd dichroic substance.
FIG. 5 shows XRD spectra of films (films 1 to 3) of the polymer liquid crystalline compound L1 monomer.
Fig. 6 shows XRD spectra of films 1 (corresponding to polarizer 1 of example 1 described below) using the 1 st dichroic material M1 and the 2 nd dichroic material O1 described below as the polymer liquid crystalline compounds L1 and 1 st dichroic material.
As can be seen from a comparison of fig. 4 to 6, among the peaks of the XRD of the film 1-2 of fig. 4, the peak O2 of the diffraction angle not observed in the XRD of the film 1-3 of fig. 5 is not observed in the XRD spectrum of the film 1 of fig. 6. Accordingly, it is determined that the condition (i) is satisfied, and the 1 st dichroic material and the 2 nd dichroic material form a crystal structure.
Next, a reason why the 1 st dichroic material and the 2 nd dichroic material form a crystal structure can be determined by satisfying the condition (ii) will be described.
The peak O2 is a peak corresponding to the 2 nd dichroic substance, and the peak M2 is a peak corresponding to the 1 st dichroic substance. Therefore, regarding the film 1 (polarizer of the present invention) containing the 1 st dichroic substance and the 2 nd dichroic substance, it can be considered that only the peak O2 and the peak M2 are detected as peaks derived from the dichroic substances.
On the other hand, it is assumed that the phenomenon in which the peak OM not observed in the XRD spectra of the films 1 to 2 and 1 to 4 is detected in the film 1 is caused by the following reason: in the polarizer, the 2 nd dichroic substance and the 1 st dichroic substance have some interaction, so that the 1 st dichroic substance and the 2 nd dichroic substance are formed with a periodically arranged structure (more specifically, a crystal structure).
Next, the condition (ii) will be specifically described using XRD spectrum. The following films 2, 2-3 and 2-4 correspond to the films 1, 1-2, 1-3 and 1-4, respectively. The details of the composition used for forming each film are described in detail in the following explanation of XRD spectrum of example 2.
Fig. 7 shows XRD spectra of films 2 to 4 using the polymer liquid crystalline compound L1 and the 1 st dichroic substance M1 described later as liquid crystalline compounds.
Fig. 8 shows XRD spectra of films 2-2 using a polymer liquid crystalline compound L1 described later as a liquid crystalline compound and a 2 nd dichroic substance O1 as a 2 nd dichroic substance.
FIG. 9 shows XRD spectra of films 2 to 3 of the polymer liquid crystalline compound L1 monomer.
Fig. 10 shows XRD spectra of films 2 using the 1 st dichroic material M1 and the 2 nd dichroic material O1 described later as the polymer liquid crystalline compound L1 and the 1 st dichroic material.
As can be seen from a comparison of fig. 7, 8, 9 and 10, among the peaks of the XRD spectrum of the film 2 of fig. 10, peaks of diffraction angles not observed in the XRD spectra of fig. 7, 8 and 9 are observed in the XRD spectrum of the film 2 of fig. 10. Accordingly, it is determined that the condition (ii) is satisfied, and the 1 st dichroic material and the 2 nd dichroic material form a crystal structure.
In the present invention, it can be confirmed that a crystal structure is formed in the polarizer by observing the surface and the cross section of the polarizer using, for example, SEM (scanning electron microscope) or TEM (transmission electron microscope). The size of the crystal structure is preferably 1 μm to 500. Mu.m, more preferably 3 μm to 400. Mu.m.
[ stabilization energy ]
In order to form the 1 st dichroic substance and the 2 nd dichroic substance into crystal structures, it is preferable to use a constant value based on the stabilization energy calculated theoretically. The stabilization energy means an energy loss (energy difference) when one of the 1 st dichroic material and the 2 nd dichroic material is incorporated into the other dichroic material in a structure in which the other dichroic material is aligned alone, and it is considered that the other dichroic material is easily incorporated into the structure because the smaller the value is, the smaller the loss is. As an example of such a method for calculating the stabilization energy, the following method can be given.
The stabilization energy can be calculated using commercially available calculation software such as AMBER11, which can calculate the molecular force field. More specifically, using crystal structure information of one kind of dichroic substance (hereinafter, also referred to as "dichroic substance a") obtained by a crystal structure analysis method such as XRD, energy when one molecule is replaced with another dichroic substance (hereinafter, also referred to as "dichroic substance B") from a super cell including a plurality of unit cells is calculated from a structure optimization calculation. Here, the use of the super cell starts from the position of the center of gravity of the dichroic substance A of one molecule present at the substitution position, including that present at the position of the center of gravity The unit cell of the dichroic substance a in the above range.
As the calculation conditions, force field information called GeneralAMBERForceField (GAFF) and charge information called RestrainedElectroStaticPotential (RESP) are used. Here, GAFF can be set by using AmberTools or the like bundled together in AMBER11, calculating a dichroic substance for each molecule under the condition that RESP uses HF/6-31G (d) of commercially available Gaussian09 or the like, and reading the result into AmberTools. Specifically, the stabilization energy is calculated as a value (X1-X2) obtained by subtracting the sum X1 of "the energy of the state in which 1 molecule of the dichroic substance a is replaced with one molecule of the super cell of the dichroic substance a" and "the energy of the dichroic substance a of one molecule" from the sum X1 of "the energy of the super cell composed of only the dichroic substance a before being replaced with one molecule of the dichroic substance B" obtained by using the above calculation conditions.
The stabilization energy (X1-X2) calculated by the above method facilitates formation of the arrangement structure of the 1 st dichroic material and the 2 nd dichroic material, and is therefore preferably less than 72kcal/mol, preferably 55kcal/mol or less, more preferably 35kcal/mol or less, from the viewpoint of obtaining a polarizer with a higher degree of orientation. The lower limit of the stabilization energy is preferably-13 kcal/mol or more.
The ratio (X1/X2) of the sum X1 to the sum X2 (hereinafter, also referred to as "stabilization energy ratio") is preferably 0.22 or more, more preferably 0.40 or more, and particularly preferably 0.60 or more, from the viewpoint of obtaining a polarizer having a higher degree of orientation, since the arrangement structure of the 1 st dichroic material and the 2 nd dichroic material is easy to form. The upper limit of the stabilized energy ratio is not particularly limited, but is usually 1.50 or less, preferably 1.30 or less.
[ method for producing polarizer ]
The method for producing the polarizer of the present invention is not particularly limited, but from the viewpoint of the degree of orientation of the obtained polarizer becoming higher, a method comprising the following steps in order (hereinafter, also referred to as "the production method") is preferable: a step of forming a coating film by applying the composition to an alignment film (hereinafter, also referred to as a "coating film forming step"); and a step of aligning the dichroic material contained in the coating film (hereinafter, also referred to as an "alignment step"). In the following, the "the degree of orientation of the obtained polarizer becomes higher" is also referred to as "the effect of the present invention is more excellent".
Hereinafter, each step will be described.
< coating film Forming Process >
The coating film forming step is a step of forming a coating film by applying the composition to an alignment film. The liquid crystalline compound in the coating film is horizontally oriented by the interaction of the orientation film and the interface modifier (in the case where the composition contains the interface modifier).
The composition can be easily applied to an alignment film by using the composition containing the solvent or by heating the composition to a liquid such as a melt.
Examples of the method for applying the composition include known methods such as roll coating, gravure coating, spin coating, bar coating, extrusion coating, direct gravure coating, reverse gravure coating, die coating, spray coating, and ink jet coating.
(alignment film)
The alignment film may be any film as long as it is a film for horizontally aligning the liquid crystalline compound contained in the composition.
Can be set by friction treatment of the film surface with an organic compound (preferably a polymer), oblique evaporation of an inorganic compound, formation of a layer having micro grooves, or accumulation of an organic compound (for example, ω -ditridecanoic acid, dioctadecyl methyl ammonium chloride, methyl stearate) based on the Langmuir-Blodgett method (LB film). Further, an alignment film that generates an alignment function by applying an electric field, a magnetic field, or light irradiation is also known. Among them, in the present invention, an alignment film formed by rubbing treatment is preferable from the viewpoint of easiness of controlling the pretilt angle of the alignment film, and a photo-alignment film formed by light irradiation is also preferable from the viewpoint of alignment uniformity.
(1) Rubbing treatment of oriented film
As a polymer material for an alignment film formed by a rubbing treatment, many documents have been described, and many commercial products are available. In the present invention, polyvinyl alcohol or polyimide and derivatives thereof are preferably used. For the alignment film, refer to the description of page 43, line 24 to page 49, line 8 of International publication No. 2001/88574A 1. The thickness of the alignment film is preferably 0.01 to 10. Mu.m, more preferably 0.01 to 1. Mu.m.
(2) Photo-alignment film
As a photo-alignment material for an alignment film formed by light irradiation, many documents and the like have been described. In the present invention, preferable examples include: an azo compound described in Japanese patent application laid-open No. 2006-285197, japanese patent application laid-open No. 2007-076839, japanese patent application laid-open No. 2007-138138, japanese patent application laid-open No. 2007-094071, japanese patent application laid-open No. 2007-121721, japanese patent application laid-open No. 2007-140465, japanese patent application laid-open No. 2007-156439, japanese patent application laid-open No. 2007-133184, japanese patent application laid-open No. 2009-109831, japanese patent application No. 3883848, and Japanese patent application No. 4151746; an aromatic ester compound described in Japanese patent application laid-open No. 2002-229039; a maleimide and/or alkenyl-substituted naphthalimide compound having a photo-alignment unit described in Japanese unexamined patent publication No. 2002-265541 and Japanese unexamined patent publication No. 2002-317013; photo-crosslinkable silane derivatives described in japanese patent No. 4205195 and japanese patent No. 4205198; and a photo-crosslinkable polyimide, polyamide or ester described in Japanese patent application laid-open No. 2003-520878, japanese patent application laid-open No. 2004-529220 or Japanese patent application laid-open No. 4162850. More preferably an azo compound, photo-crosslinkable polyimide, polyamide or ester.
A photo-alignment film formed of the above material is irradiated with linearly polarized light or non-polarized light to produce a photo-alignment film.
In the present specification, "linearly polarized light irradiation" and "unpolarized light irradiation" refer to an operation for photoreacting a photoalignment material. The wavelength of the light to be used varies depending on the photo-alignment material to be used, and is not particularly limited as long as it is a wavelength required for the photoreaction. The peak wavelength of light used for irradiation of light is preferably 200nm to 700nm, and more preferably ultraviolet light having a peak wavelength of 400nm or less.
Examples of the light source used for the light irradiation include commonly used light sources such as tungsten lamp, halogen lamp, xenon flash lamp, mercury-xenon lamp, and carbon arc lamp, and various lasers [ e.g., semiconductor laser, helium-neon laser, argon ion laser, helium-cadmium laser, and YAG (yttrium-aluminum-garnet) laser ], light emitting diode, and cathode ray tube.
As a method of obtaining linearly polarized light, a method using a polarizing plate (for example, an iodine polarizing plate, a dichroic substance polarizing plate, and a wire grid polarizing plate), a method using a reflective polarizer using a prism element (for example, a gram-thomson prism) or brewster angle, or a method using light emitted from a laser light source having polarized light can be employed. Further, a filter, a wavelength conversion element, or the like may be used to selectively irradiate only a desired wavelength.
In the case where the irradiated light is linearly polarized light, a method of irradiating light perpendicularly or obliquely to the surface of the alignment film from the upper surface or the back surface thereof is employed. The incident angle of light varies depending on the photo-alignment material, but is preferably 0 to 90 ° (perpendicular), preferably 40 to 90 °.
In the case of unpolarized light, the orientation film is obliquely irradiated with unpolarized light. The incident angle is preferably 10 to 80 °, more preferably 20 to 60 °, and still more preferably 30 to 50 °.
The irradiation time is preferably 1 minute to 60 minutes, more preferably 1 minute to 10 minutes.
In the case where patterning is required, a method of applying light irradiation using a photomask a required number of times in patterning or a method of writing a pattern by laser scanning can be employed.
< alignment procedure >
The alignment step is a step of aligning a dichroic material contained in the coating film. Thus, the polarizer of the present invention can be obtained. In the alignment step, it is considered that the dichroic material is aligned along the liquid crystal compound aligned by the alignment film.
The orientation process may have a drying process. The drying treatment can remove components such as a solvent from the coating film. The drying treatment may be performed by leaving the coating film at room temperature for a predetermined period of time (for example, natural drying), or may be performed by heating and/or air blowing.
Here, the dichroic material contained in the composition may be aligned by the coating film forming step or the drying treatment. For example, in the case where the composition is prepared as a coating liquid containing a solvent, the coating film may be dried to remove the solvent from the coating film, whereby the dichroic material contained in the coating film is aligned, and the polarizer of the present invention is obtained.
The orientation step preferably includes a heat treatment. Thereby, the dichroic material contained in the coating film is further aligned, and the degree of alignment of the resulting polarizer becomes higher.
The heat treatment is preferably 10 to 250℃and more preferably 25 to 190℃in view of the manufacturing suitability and the like. The heating time is preferably 1 to 300 seconds, more preferably 1 to 60 seconds.
The orientation process may have a cooling process performed after the heating process. The cooling treatment is a treatment of cooling the heated coating film to about room temperature (20 to 25 ℃). Therefore, the orientation of the dichroic material contained in the coating film is further fixed, and the degree of orientation of the resulting polarizer is further improved. The cooling method is not particularly limited, and may be performed by a known method.
Through the above steps, the polarizer of the present invention can be obtained.
[ other procedures ]
The method of the present invention may include a step of curing the polarizer after the orientation step (hereinafter, also referred to as a "curing step").
The curing step is performed by heating and/or light irradiation (exposure), for example. Among them, the curing step is preferably performed by light irradiation.
The light source used for curing may be various light sources such as infrared light, visible light, and ultraviolet light, but ultraviolet light is preferable. In addition, when curing, ultraviolet rays may be irradiated while heating, or ultraviolet rays may be irradiated via a filter that transmits only a specific wavelength.
The exposure may be performed under a nitrogen atmosphere. In the case of curing the polarizer by radical polymerization, exposure to light in a nitrogen atmosphere is preferable because inhibition of polymerization by oxygen is reduced.
[ laminate ]
The laminate of the present invention comprises a substrate, an alignment film provided on the substrate, and the polarizer of the present invention provided on the alignment film.
The laminate of the present invention may have a λ/4 plate on the polarizer of the present invention.
The laminate of the present invention may have a barrier layer between the polarizer of the present invention and the λ/4 plate.
The layers constituting the laminate of the present invention will be described below.
[ substrate ]
The substrate may be appropriately selected, and examples thereof include glass and a polymer film. The light transmittance of the base material is preferably 80% or more.
In the case of using a polymer film as a substrate, an optically isotropic polymer film is preferably used. Specific examples and preferred modes of the polymer can be applied to those described in paragraph [0013] of Japanese patent application laid-open No. 2002-022942. In addition, a polymer which easily exhibits birefringence such as polycarbonate or polysulfone, which has been known conventionally, may be used, and the molecule described in International publication No. 2000/26705 is modified to reduce the appearance.
[ alignment film ]
Since the alignment film is described above, a description thereof will be omitted.
[ polarizer ]
Since the polarizer of the present invention is described above, the description thereof will be omitted.
[ lambda/2 plate ]
The "λ/4 plate" is a plate having a λ/4 function, and specifically, a plate having a function of converting linearly polarized light of a certain specific wavelength into circularly polarized light (or converting circularly polarized light into linearly polarized light).
For example, the λ/4 plate has a single-layer structure, specifically, a stretched polymer film, a retardation film having an optically anisotropic layer having a λ/4 function provided on a support, and the λ/4 plate has a multilayer structure, specifically, a wide-band λ/4 plate obtained by laminating a λ/4 plate and a λ/2 plate.
The lambda/4 plate and the polarizer of the invention may be arranged in contact, or other layers may be arranged between the lambda/4 plate and the polarizer of the invention. Examples of such a layer include an adhesive layer, and a barrier layer for ensuring adhesion.
[ Barrier layer ]
In the case where the laminate of the present invention is provided with a barrier layer, the barrier layer is provided between the polarizer of the present invention and the λ/4 plate. In the case where a layer other than the barrier layer (for example, an adhesive layer or an adhesive layer) is provided between the polarizer of the present invention and the λ/4 plate, the barrier layer can be provided between the polarizer of the present invention and the other layer.
The barrier layer is also called a gas barrier layer (oxygen barrier layer), and has a function of protecting the polarizer of the present invention from gas such as oxygen in the atmosphere, moisture, or a compound contained in an adjacent layer.
For the barrier layer, for example, references can be made to paragraphs [0014] to [0054] of JP-A2014-159724, paragraphs [0042] to [0075] of JP-A2017-121721, paragraphs [0045] to [0054] of JP-A2017-115076, paragraphs [0010] to [0061] of JP-A2012-213938, and paragraphs [0021] to [0031] of JP-A2005-169994.
[ use ]
The laminate of the present invention can be used as a polarizing element (polarizer), for example, as a linear polarizer or a circular polarizer.
In the case where the laminate of the present invention does not have the above-described optically anisotropic layer such as a λ/4 plate, the laminate can be used as a linear polarizer.
On the other hand, in the case where the laminate of the present invention has the above λ/4 plate, the laminate can be used as a circularly polarizing plate.
[ image display device ]
The image display device of the present invention includes the polarizer of the present invention or the laminate of the present invention.
The display element used in the image display device of the present invention is not particularly limited, and examples thereof include a liquid crystal cell, an organic electroluminescence (hereinafter, abbreviated as "EL") display panel, and a plasma display panel.
Among them, a liquid crystal cell or an organic EL display panel is preferable, and a liquid crystal cell is more preferable. That is, as the image display device of the present invention, a liquid crystal display device using a liquid crystal cell as a display element and an organic EL display device using an organic EL display panel as a display element are preferable, and a liquid crystal display device is more preferable.
[ liquid Crystal display device ]
As an example of the image display device of the present invention, that is, a liquid crystal display device, a mode having the polarizer and the liquid crystal cell of the present invention described above is preferable. More preferably, a liquid crystal display device having the laminate of the present invention (excluding the lambda/4 plate) and a liquid crystal cell is provided.
In the present invention, the laminate of the present invention is preferably used as a front polarizing element among polarizing elements provided on both sides of a liquid crystal cell, and more preferably used as front and rear polarizing elements.
Hereinafter, a liquid crystal cell constituting the liquid crystal display device will be described in detail.
< liquid Crystal cell >
The liquid crystal cell used In the liquid crystal display device is preferably a VA (Vertical Alignment: vertical alignment) mode, an OCB (Optically Compensated Bend: optically compensatory bend) mode, an IPS (In-Plane-Switching) mode, or a TN (Twisted Nematic) mode, but is not limited thereto.
In a TN mode liquid crystal cell, when no voltage is applied, rod-like liquid crystal molecules are aligned substantially horizontally and further twisted at 60 to 120 degrees. TN-mode liquid crystal cells are used as color TFT (Thin Film Transistor: thin film transistor) liquid crystal display devices in many documents.
In the VA mode liquid crystal cell, when no voltage is applied, the rod-like liquid crystal molecules are aligned substantially vertically. The VA mode liquid crystal cell includes (1) a VA mode liquid crystal cell in which rod-like liquid crystal molecules are aligned substantially vertically when no voltage is applied and substantially aligned horizontally when a voltage is applied (japanese patent application laid-open No. 2-176825): (2) In order to expand the viewing angle, VA-mode multi-domain (MVA-mode) liquid crystal cells (SID 97, digest of tech. papers 28 (1997) 845); (3) Liquid crystal cells of a mode (n-ASM mode) in which rod-like liquid crystal molecules are aligned substantially vertically when no voltage is applied and twisted and multi-domain aligned when a voltage is applied (described in treatises 58 to 59 (1998) of japan liquid crystal seminar); and (4) a SURVIVA L mode liquid crystal cell (published in LCD International 98). Further, the Polymer may be any of PVA (Patterned Vertical Alignment: pattern homeotropic alignment), photo alignment (Optical Alignment) and PSA (Polymer-Sustained Alignment: polymer continuous alignment). Details of these modes are described in detail in Japanese patent application laid-open No. 2006-215326 and Japanese patent application laid-open No. 2008-538819.
In the IPS mode liquid crystal cell, rod-like liquid crystal molecules are aligned substantially parallel to a substrate, and the liquid crystal molecules respond in an in-plane manner by applying an electric field parallel to the substrate surface. The IPS mode displays black without an electric field applied thereto, and the absorption axes of the pair of upper and lower polarizers are orthogonal to each other. Methods of reducing light leakage at the time of black display in an oblique direction and improving the angle of view using an optical compensation sheet are disclosed in Japanese patent application laid-open No. 10-054982, japanese patent application laid-open No. 11-202323, japanese patent application laid-open No. 9-292522, japanese patent application laid-open No. 11-133408, japanese patent application laid-open No. 11-305217, japanese patent application laid-open No. 10-307291, and the like.
[ organic EL display device ]
As an example of the image display device of the present invention, that is, the organic EL display device, for example, a mode having the polarizer, λ/4 plate, and organic EL display panel of the present invention described above in this order from the viewing side is preferable.
More preferably, the laminate and the organic EL display panel of the present invention having a λ/4 plate are provided in this order from the viewing side. In this case, the laminate is provided with a base material, an alignment film, the polarizer of the present invention, a barrier layer and a λ/4 plate, which are provided as needed, in this order from the viewing side.
The organic EL display panel is a display panel configured by using an organic EL element in which an organic light-emitting layer (organic electroluminescent layer) is sandwiched between electrodes (between a cathode and an anode). The structure of the organic EL display panel is not particularly limited, and a known structure may be employed.
Examples (example)
Hereinafter, the present invention will be described in more detail with reference to examples. The materials, amounts used, ratios, processing contents, processing order, and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. Accordingly, the scope of the present invention should not be construed as being limited by the embodiments shown below.
Synthesis example 1
The 1 st dichroic substance M1 is synthesized as follows.
[ chemical formula 11]
12.6g of 4-nitrophenol, 20.0g of 9-bromononanol and 13.8g of potassium carbonate were dissolved in 30ml of N, N-dimethylacetamide (DMAc), and the mixture was stirred at 105℃for 2 hours in an external apparatus. Cooled to room temperature and washed separately in ethyl acetate/10% aqueous ammonium chloride. After drying the organic layer with magnesium sulfate, concentration was performed using a rotary evaporator to obtain a brown liquid (M1-1).
Subsequently, 25ml of DMAc was added to the obtained (M1-1), and the mixture was stirred in an ice bath. The temperature of the reaction system was maintained at 15℃or lower and 9.5g of propionyl chloride was added dropwise, and after the addition, the mixture was stirred at room temperature for 1 hour. Ethyl acetate/10% ammonium chloride aqueous solution was added thereto to conduct liquid separation washing. After drying over magnesium sulfate, concentration was performed using a rotary evaporator to obtain a brown liquid (M1-2).
15.2g of Fe powder, 7.2g of ammonium chloride, 20ml of 2-propanol and 10ml of water were mixed, and the mixture was refluxed at 105℃in an external apparatus. To the refluxed system was added dropwise a yellow solid (M1-2) dissolved in 30ml of ethyl acetate under heating. After the end of the addition, the reaction was carried out for 30 minutes under reflux. After cooling to room temperature, the iron powder was removed by filtration through celite, the filtrate was separated with ethyl acetate/water, and the organic layer was washed 3 times with water.
The organic layer was concentrated using a rotary evaporator, and 15ml of THF (tetrahydrofuran) and 15ml of ethyl acetate were added. To this solution, a mixture of 240ml of water and 20ml of concentrated hydrochloric acid was added dropwise to give 15.3g of the objective substance (M1-3).
NMR (Nuclear Magnetic Resonance: nuclear magnetic resonance) data (DMSO-d 6) δ:1.03 (t, 3H), 1.25-1.48 (m, 11H), 1.58 (m, 2H), 1.71 (m, 2H), 2.30 (m, 2H), 3.97 (m, 4H), 7.01 (d, 2H), 7.29 (d, 2H), 10.04 (br-s, 3H)
The 2-aminothiophene hydrochloride was synthesized from 2-nitrothiophene according to the method described in the literature (Journal of Medicinal Chemistry, 2005, volume 48, page 5794).
6.2g of (M1-3) thus obtained was added to a mixture of 15ml of 12mol/L hydrochloric acid, 30ml of water and 30ml of THF, and the mixture was cooled to an internal temperature of 5℃or lower, whereby 1.4g of sodium nitrite was dissolved and added dropwise to 9ml of water. The mixture was stirred at an internal temperature of 5℃or lower for 1 hour to prepare a diazonium salt solution.
Then, 2.4g of 2-aminothiophene hydrochloride was dissolved in 12ml of water and 6ml of hydrochloric acid, and the diazonium salt solution prepared above was added dropwise at an internal temperature of 0 ℃. The reaction solution was allowed to warm to room temperature and stirred for 2 hours.
The precipitated solid was filtered off and dried, thereby obtaining 6.3g of a red-orange solid (M1-4).
NMR data (DMSO-d 6) delta: 1.01 (t, 3H), 1.29-1.40 (m, 11H), 1.55 (m, 2H), 1.69 (m, 2H), 2.29 (m, 2H), 3.17 (s, 2H), 3.97 (m, 4H), 6.88 (br-s, 1H), 6.97 (d, 2H), 7.39 (d, 2H), 7.85 (m, 1H)
In the formula, "Boc" means t-butoxycarbonyl group.
5.6g of (M1-4) obtained in the above was suspended and dissolved in 100ml of acetic acid, and 1.5g of sodium thiocyanate was added at room temperature. Water cooling was performed, and 2.0g of bromine was added dropwise while maintaining the internal temperature at 20℃or lower.
After stirring at room temperature for 2 hours, 100ml of water was added, and the resulting solid was filtered off and dried, thereby obtaining 5.3g of a black solid (M1-5).
NMR data (CDCl) 3 )δ：1.14(t、3H)、1.30-1.50(m、11H)、1.60(m、6H)、1.81(m、2H)、2.32(q、2H)、4.04(m、4H)、5.31(br、2H)、6.95(d、2H)、7.66(s、1H)、7.78(d、2H)
4.7g of (M1-5) obtained in the above was added to 6ml of hydrochloric acid and 6ml of acetic acid, 5ml of an aqueous solution of 0.72g of sodium nitrite was added dropwise to the mixture at 0℃or lower under ice-cooling, and after stirring for 1 hour, 0.52mg of amidosulfuric acid was added to obtain a diazonium salt solution.
While maintaining a solution of 2.2g of N-ethyl-N- (2-acryloyloxyethyl) aniline in 10ml of methanol at 0℃or lower, a diazonium salt solution was added dropwise. After stirring for 1 hour, 30ml of water was added and the resulting solid was filtered off. Purification by column afforded 0.6g of the compound as a green solid (dichroic substance M1 st).
N-ethyl-N- (2-acryloyloxyethyl) aniline was synthesized from N-ethylaniline by a known method and using U.S. Pat. No. 7601849.
NMR data (CDCl) 3 )δ：1.14(t、3H)、1.26(t、3H)、1.29(br-s、8H)、1.49(m、2H)、1.64(m、2H)、1.82(m、2H)，2.33(m、2H)、3.58(m、2H)、3.77(m、2H)、4.07(m、4H)、4.40(m、2H)、5.90(dd、1H)、6.15(dd、1H)、6.40(dd、1H)、6.82(d、2H)、7.00(d、2H)、7.88(m、3H)、7.95(d、2H)
Synthesis example 2
The 2 nd dichroic dye compound O1 was synthesized as follows.
[ chemical formula 12]
To 27g of acetamido group was added 100ml of water, cooled to 0℃and stirred. 66ml of concentrated hydrochloric acid was added dropwise to the solution. Next, an aqueous solution of 12.5g of sodium nitrite (Wako Pure Chemical, manufactured by ltd. Below) dissolved in 30ml of water was added dropwise. The internal temperature is kept at 0 ℃ to 5 ℃. After the completion of the dropwise addition, stirring was performed at 0℃or lower for 1 hour to prepare a diazonium salt solution.
To 17.5g of phenol, 20ml of methanol was added and stirred to dissolve the same. To this solution was added an aqueous solution of NaOH28.8g dissolved in 150ml of water, cooled to 0℃and stirred. To this solution was added dropwise the diazonium salt solution prepared by the above method at 0℃to 5 ℃. After the completion of the dropwise addition, stirring was carried out at 5℃for 1 hour, followed by stirring at room temperature for 1 hour to complete the reaction. Next, an aqueous solution of Na OH36.0g dissolved in 150ml of water was added, and heated under reflux for 3 hours. After the completion of the reaction, an aqueous hydrochloric acid solution was added to adjust to ph=7.0 after cooling to room temperature, and the precipitated crystals were filtered, thereby obtaining 40.2g of compound O1-1 (yield: 87.2%, brown crystals).
N-ethyl-N- (2-acryloyloxyethyl) aniline was synthesized from N-ethylaniline by a known method using U.S. Pat. No. 7601849.
To 5.0g of Compound O1-1 were added 100ml of acetic acid, 10ml of water and 20ml of methanol, cooled to 0℃and stirred. To this solution, 7ml of concentrated hydrochloric acid was added dropwise. Subsequently, an aqueous solution of 1.8g of sodium nitrite dissolved in 5ml of water was added dropwise. The internal temperature is maintained at 0 to 5 ℃. After the completion of the dropwise addition, stirring was carried out at 0℃or lower for 1 hour to adjust the diazonium salt solution.
To 8.4g of the above-synthesized N-ethyl-N- (2-acryloyloxyethyl) aniline, 7.7g of sodium acetate, 100ml of methanol and 100ml of water were added and stirred to dissolve the mixture, cooled to 0℃and stirred. To this solution, a diazonium salt solution adjusted by the above method was added dropwise at 0 to 5 ℃. After the completion of the dropwise addition, stirring was carried out at 5℃for 1 hour, followed by stirring at room temperature for 1 hour to complete the reaction. The precipitated group was filtered off to obtain 6.2g of Compound O1-2 (yield: 86.8%, brown crystals).
After 50.0g of 1-bromononanol was dissolved in 500ml of ethyl acetate, 26.5g of triethylamine was added dropwise and stirring was carried out at 5 ℃. After 22.8g of propionyl chloride was added dropwise, the reaction was stirred at room temperature for 1 hour to complete the reaction. After completion of the reaction, 175ml of water was added to separate the solution, and 10g of magnesium sulfate was added to the organic layer to dehydrate the solution. The resulting organic layer was concentrated using a rotary evaporator to give propionic acid-9-bromononyl ester (52 g, colorless transparent liquid).
To compound O1-2 (7.2 g), potassium carbonate (7.7 g, 0.014 mmol) and potassium iodide (0.15 g, 0.002 mol) were added dimethylacetamide (72 ml), and the mixture was heated and stirred at 80 ℃. To this solution, 8.4g of the 9-bromononyl propionate synthesized in the above was added dropwise. After the completion of the dropwise addition, heating was performed at 80℃and stirring was performed for 4 hours to complete the reaction. After the completion of the reaction, the reaction solution was poured into water, and the precipitated crystals were filtered and washed with water. The crystals were separated and purified by silica gel column chromatography (eluent: chloroform, next chloroform/ethyl acetate=50/1). The crystals precipitated by adding methanol to the residue were filtered, washed with methanol, and dried. Thus, 5.5g of a 2 nd dichroic substance O1 (orange crystal) was obtained.
NMR data (CDCl) 3 )δ：1.13(t、3H)、1.25(t、3H)、1.29(br-s、8H)、1.49(m、2H)、1.64(m、2H)、1.82(m、2H)、2.33(q、2H)、2.53(m、2H)、2.73(t、2H)、4.03(q、4H)、4.38(t、2H)、5.86(d、1H)、6.12(dd、1H)、6.43(d、1H)、6.83(d、2H)、7.00(d、2H)、7.94(m、8H)
Synthesis example 3
The 3 rd dichroic substance Y1 is synthesized as follows.
First, 4-hydroxybutyl acrylate (20 g) and methanesulfonyl chloride (16.8 g, msCl) were dissolved in ethyl acetate (90 mL), and then triethylamine (16.4 g, NEt) was added dropwise while cooling in an ice bath 3 ). Then, after stirring at room temperature for 2 hours, 1N HCl was added to separate the liquid. The obtained organic layer was distilled under reduced pressure to obtain compound y1 (30 g) having the following structure.
[ chemical formula 13]
/>
Then, the 3 rd dichroic substance Y1 was synthesized in the following way.
[ chemical formula 14]
First, compound y2 (10 g) was synthesized according to literature (chem. Eur. J. 2004.10.2011).
Compound y2 (10 g) was dissolved in water (300 mL) and hydrochloric acid (17 mL), cooled in an ice bath, and sodium nitrite (3.3 g) was added thereto and stirred for 30 minutes. After further addition of amidosulfuric acid (0.5 g), m-toluidine (5.1 g) was added and stirred at room temperature for 1 hour. After stirring, a solid obtained by neutralization with hydrochloric acid was recovered by suction filtration to obtain compound y2 (3.2 g).
Compound y2 (1 g) was dissolved in a THF solution composed of tetrahydrofuran (30 mL, THF), water (10 mL) and hydrochloric acid (1.6 mL), cooled in an ice bath, sodium nitrite (0.3 g) was added, and after stirring for 30 minutes, amidosulfuric acid (0.5 g) was also added. Phenol (0.4 g) was dissolved in potassium carbonate (2.76 g) and water (50 mL), and after cooling in an ice bath, the THF solution was added dropwise, and the mixture was stirred at room temperature for 1 hour. After stirring, water (200 mL) was added and the resulting compound y3 (1.7 g) was suction filtered.
Compound y3 (0.6 g), compound y1 (0.8 g) and potassium carbonate (0.95 g) were dissolved in DMAc (30 mL, dimethylacetamide), and stirred at 90 ℃ for 3.5 hours. After stirring, water (300 mL) was added, and the resulting solid was suction-filtered to obtain a 3 rd dichromatic substance Y1 (0.3 g).
Synthesis example 4
The polymer liquid crystalline compound L1 was prepared in the following order.
(Synthesis of Compound L1-2)
[ chemical formula 15]
To a solution (300 mL) of butyl p-hydroxybenzoate (201 g) in N, N-Dimethylformamide (DMF) was added 2-chloroethoxyethoxyethanol (244 g) and potassium carbonate (200 g). After stirring at 95℃for 9 hours, toluene (262 mL) and water (660 mL) were added, and concentrated hydrochloric acid (147 g) was added dropwise. After stirring for 10 minutes, the reaction solution was allowed to stand and washed by a liquid separation operation. To the resulting organic layer were added 28 mass% sodium methoxide methanol solution (500 g) and water (402 mL), and the mixture was stirred at 50℃for 2 hours. Then, the organic solvent was distilled off by concentration, and water (402 mL) was added thereto, and concentration was performed again at 50 ℃ until the weight became 1.13 kg. To the resulting solution was added water (478 mL), and concentrated hydrochloric acid (278 g) was added dropwise. Ethyl acetate (1.45 kg) was added thereto, stirred at 30℃for 10 minutes, and the aqueous layer was removed by a liquid separation operation. Then, a 20 mass% aqueous solution of saline (960 mL) was added, stirred at 30℃for 10 minutes, and the aqueous layer was removed by a liquid separation operation. N-methylpyrrolidone (824 g) was added to the obtained organic layer, and the mixture was concentrated at 70℃for 4 hours to obtain 1.13kg of an N-methylpyrrolidone solution containing the compound (L1-1). The next step was carried out using 1085g of the N-methylpyrrolidone solution containing the obtained (L1-1).
To a solution (1085 g) of N-methylpyrrolidone (NMP) containing the obtained (L1-1) were added N, N-dimethylaniline (189 g) and 2, 6-tetramethylpiperazine (1.5 g), and after cooling the internal temperature, chlorine acrylate (122 g) was added dropwise so that the internal temperature did not exceed 10 ℃. After stirring at an internal temperature of 10℃for 2 hours, methanol (81 g) was added dropwise and stirred for 30 minutes. Ethyl acetate (1.66 kg), 10 mass% saline (700 mL) and 1N hydrochloric acid water (840 mL) were added thereto, and the aqueous layer was removed by a liquid separation operation. Then, 10 mass% aqueous saline (800 mL) was added, stirred at 30℃for 10 minutes, and the aqueous layer was removed by a liquid separation operation. Then, a 20 mass% aqueous solution of saline (800 mL) was added, stirred at 30℃for 10 minutes, and the aqueous layer was removed by a liquid separation operation. To the obtained organic layer was added a mixed solvent of hexane/isopropyl alcohol (1780 mL/900 mL), and after cooling to 5 ℃ and stirring for 30 minutes, filtration was performed, whereby 209g (3-step yield 65%) of a white solid compound (L1-2) was obtained. In the structural formula, bu represents butyl.
1 H-NMR (solvent: CDCl) 3 )δ(ppm)：3.67-3.78(m，6H)，3.87-3.92(m，2H)，4.18-4.23(m，2H)，4.31-4.35(m，2H)，5.80-5.85(m，1H)，6.11-6.19(m，1H)，6.40-6.46(m，1H)，6.93-6.98(m，2H)，8.02-8.07(m，2H)
(Synthesis of Compound L1-3)
[ chemical formula 16]
/>
To a solution of methanesulfonyl chloride (MsCl) (73.4 mmol,5.7 mL) in Tetrahydrofuran (THF) (70 mL) was added dibutylhydroxytoluene (BHT) (200 mg), and the internal temperature was cooled to-5 ℃. A THF solution of compound (L1-2) (66.7 mmol,21.6 g) and Diisopropylethylamine (DIPEA) (75.6 mmol,13.0 mL) was added dropwise thereto so that the internal temperature did not rise above 0 ℃. After stirring at-5℃for 30 minutes, N-dimethyl-4-aminopyridine (DMAP) (200 mg) was added, and a solution of diisopropylethylamine (75.6 mmol,13.0 mL), 4-hydroxy-4' -methoxybiphenyl (60.6 mmol, 12.1 g) in Tetrahydrofuran (THF) and dimethylacetamide (DMAc) was added dropwise so that the internal temperature did not rise above 0 ℃. Then, the mixture was stirred at room temperature for 4 hours. After the reaction was stopped by adding methanol (5 mL), water and ethyl acetate were added. The solvent was removed from the organic layer extracted with ethyl acetate by a rotary evaporator, and purification was performed by column chromatography using ethyl acetate and hexane to give 18.7g (yield 61%) of compound (L1-3) as a white solid. In the structural formula, me represents a methyl group.
1 H-NMR (solvent: CDCl) 3 )δ(ppm)：3.65-3.82(m，6H)，3.85(s，3H)，3.85-3.95(m，2H)，4.18-4.28(m，2H)，4.28-4.40(m，2H)，5.82(dd，1H)，6.15(dd，1H)，6.43(dd，1H)，6.90-7.05(m，4H)，7.20-7.30(m，2H)，7.45-7.65(m，4H)，8.10-8.20(m，2H)
The following compound (L1-b) was contained as an impurity.
[ chemical formula 17]
n is an integer other than 3 (L1-b)
(Synthesis of Compound L1-23)
[ chemical formula 18]
Methyl 4- (4-hydroxyphenyl) benzoate was prepared by the process described in Journal of Polymer Science, part a: the synthesis was carried out by the method described in Polymer chemistry 2012, vol.50, p.3936-3943.
To a solution of methanesulfonyl chloride (MsCl) (54.8 mmol,6.27 g) in ethyl acetate (44 mL) was added 2, 6-tetramethylpiperidine 1-oxyl (68 mg), and the internal temperature was cooled to-5 ℃. A THF solution of the compound (L1-2) (52.6 mmol,17.1 g) synthesized as described above and Diisopropylethylamine (DIPEA) (57.0 mol,7.36 g) was added dropwise thereto so that the internal temperature did not rise to 0℃or higher. After stirring at-5℃for 30 minutes, a solution of methyl 4- (4-hydroxyphenyl) benzoate (43.8 mmol,10.0 g) in DMAc, N-methyl-imidazole (NMI) (1.8 g) and diisopropylethylamine (75.6 mmol,13.0 mL) were added dropwise so that the internal temperature did not rise above 0 ℃. Then, the mixture was stirred at room temperature for 4 hours. The reaction was stopped by adding water and ethyl acetate. The organic layer extracted with ethyl acetate was separated and the solvent was removed by a rotary evaporator, and purified by column chromatography using ethyl acetate and hexane to give 20.4g (yield 87%) of compound (L1-23) as a white solid.
1 H-NMR (solvent: CDCl) 3 )δ(ppm)：3.68-3.80(m，6H)，3.87-3.95(m，2H)，3.95(s，3H)，4.20-4.27(m，2H)，4.31-4.37(m，2H)，5.83(dd，1H)，6.16(dd，1H)，6.43(dd，1H)，6.97-7.05(m，2H)，7.28-7.35(m，2H)，7.64-7.72(m，4H)，8.08-8.20(m，4H)
As impurities, the following compounds (L1-b 2) were contained.
[ chemical formula 19]
n is an integer other than 3 (L1-2 b)
(Synthesis of Polymer liquid Crystal Compound L1)
[ chemical formula 20]
Compound (L1-3) (84 g), compound (L1-23) (21 g), and dibutylhydroxytoluene (BHT) (158 mg) were dissolved in anisole (337 g). Dimethyl 2,2' -azobis (2-methylpropionate) (1660 mg) (trade name "V-601") was added thereto at room temperature and stirred. The anisole solution thus obtained was added dropwise to anisole (84 g) heated to 80℃under nitrogen atmosphere over 2 hours, and after the completion of the addition, the mixture was stirred at 80℃for 4 hours. The obtained reaction solution was added dropwise to methanol (1080 mL), and after collecting a precipitate by filtration, the residue was washed with acetonitrile to obtain 100g of a white solid compound (high molecular liquid crystalline compound L1) (yield 95%). The weight average molecular weight (Mw) of the obtained polymer liquid crystalline compound L1 was 13300.
The molecular weight was calculated by Gel Permeation Chromatography (GPC) in terms of polystyrene, 3 columns of TOSOH TSKgelSuperAWM-H (manufactured by Tosoh Corporation) were used, and N-methylpyrrolidone was used as the solvent.
[ example 1]
[ production of transparent support 1]
An alignment film coating liquid having the following composition was continuously applied to a TAC substrate (product name "TG40", manufactured by Fujifilm Corporation) having a thickness of 40. Mu.m, by means of a bar of # 8. Then, the transparent support 1 having a polyvinyl alcohol (PVA) oriented film having a thickness of 0.8 μm formed on the TAC substrate was obtained by drying with warm air at 100 ℃ for 2 minutes.
The modified polyvinyl alcohol was added to the alignment film coating liquid so that the solid content concentration became 4 mass%.
Modified polyvinyl alcohol
[ chemical formula 21]
[ production of oriented film 1]
To 1 part by mass of the photo-alignment material E-1 having the following structure, 41.6 parts by mass of butoxyethanol, 41.6 parts by mass of dipropylene glycol monomethyl ether and 15.8 parts by mass of pure water were added, and the resulting solution was pressure-filtered through a membrane filter to prepare a composition 1 for forming an alignment film, having a thickness of 0.45. Mu.m.
Next, the obtained composition 1 for forming an alignment film was coated on the transparent support 1, and dried at 60 ℃ for 1 minute. Then, the obtained coating film was irradiated with linearly polarized ultraviolet rays (illuminance 4.5mW, irradiation amount 500 mJ/cm) 2 ) An alignment film 1 (described as azo (E-1) in Table 1 below) was produced. ).
[ chemical formula 22]
E-1
[ production of polarizer ]
The following polarizer-forming composition 1 was continuously applied to the obtained alignment film 1 with a bar of #7, thereby forming a coating film 1.
Then, the coating film 1 was heated at 140℃for 90 seconds, and the coating film 1 was cooled to room temperature (23 ℃).
Then, the mixture was heated at 90℃for 60 seconds, and cooled again to room temperature.
Then, a high-pressure mercury lamp was used at an illuminance of 28mW/cm 2 The polarizer 1 (film 1) was produced on the alignment film 1 by irradiation for 60 seconds.
[ chemical formula 23]
[ formation of transparent resin layer (Barrier layer) 1 ]
On polarizer 1, the following curable composition 1 was continuously coated with a bar of #2 and dried at 60℃for 5 minutes.
Then, a high-pressure mercury lamp was used at an illuminance of 28mW/cm 2 The curable composition 1 was cured by irradiation for 60 seconds under the irradiation condition of (a) to prepare a laminate in which a transparent resin layer (barrier layer) 1 was formed on the polarizer 1. Thus, a laminate of example 1 was obtained.
The transparent resin layer 1 was cut in cross section by a dicing saw, and when the film thickness was measured by observation with a scanning electron microscope (Scan ning Electron Microscope: SEM), the film thickness was about 1.0. Mu.m.
KAYARADPET-30
[ chemical formula 24]
[ examples 2 to 19, comparative examples 1 to 2]
A laminate having a polarizer was produced in the same manner as in example 1, except that the composition for forming a polarizer described in table 1 was used instead of the composition for forming a polarizer 1.
[ Polymer liquid Crystal Compound ]
Hereinafter, the components used in each example are collectively shown.
[ chemical formula 25]
[ chemical formula 26]
The maximum absorption wavelength of the 1 st dichroic substance M is shown below.
M1：591nm
M2：591nm
M3：592nm
M4：589nm
M5：608nm
M6：592nm
M7：591nm
M8：590nm
M9：604nm
[ chemical formula 27]
The maximum absorption wavelength of the 2 nd dichroic substance M is shown below.
O1：471nm
O2：484nm
O3：455nm
O 4：459nm
O5：471nm
O6：488nm
O 7：471nm
O8：478nm
O9：477nm
O10：479nm
O11：477nm
O12：472nm
O13：460nm
O14：467nm
O15：477nm
O16：460nm
O17：484nm
[ chemical formula 28]
The maximum absorption wavelength of the 3 rd dichroic substance Y is shown below.
Y1：418nm
Y2：418nm
Y3：447nm
[ chemical formula 29]
[ evaluation ]
The polarizers of examples and comparative examples obtained as described above were evaluated as follows.
[ orientation ]
Each laminate of examples and comparative examples was set on a sample stage with a linear polarizer inserted on the light source side of an optical microscope (manufactured by Nikon Corporation, product name "ECL ipsec 600 POL"), absorbance of the polarizer in the wavelength region of 380nm to 780nm was measured at 1nm intervals using a multichannel spectroscope (manufactured by OptoSirius corporation, product name "QE 65000"), and an average value in the range from 400nm to 700nm was calculated as the degree of orientation by the following formula. The results are shown in table 1.
Degree of orientation: s= ((Az 0/Ay 0) -1)/((Az 0/Ay 0) +2)
Az0: absorbance of polarized light in the direction of the absorption axis of the polarizer
Ay0: absorbance of polarized light in the direction of the polarization axis of the polarizer
[ maximum absorption wavelength ]
< maximum absorption wavelength of example 1 >
(film 1-2)
The following composition 1-2 for forming a polarizer was continuously applied to the alignment film 1 obtained in the above manner by a bar #7, thereby forming a coating film 1-2.
Then, the coating film 1-2 was heated at 140℃for 90 seconds, and the coating film 1-2 was cooled to room temperature (23 ℃).
Then, the mixture was heated at 80℃for 60 seconds and cooled again to room temperature.
Then, a high-pressure mercury lamp was used at an illuminance of 28mW/cm 2 The film 1-2 was produced by irradiation under the irradiation condition for 60 seconds.
Film 1-2 does not contain dichroic substance M1.
(films 1-4)
The following polarizer-forming compositions 1 to 4 were continuously applied to the alignment film 1 obtained in the above manner by a bar #7, thereby forming coating films 1 to 4.
Then, the coating film 1-4 was heated at 140℃for 90 seconds, and the coating film 1-2 was cooled to room temperature (23 ℃).
Then, the mixture was heated at 90℃for 60 seconds, and cooled again to room temperature.
Then, a high-pressure mercury lamp was used at an illuminance of 28mW/cm 2 The films 1 to 4 were produced by irradiation for 60 seconds under the irradiation conditions.
Films 1-4 do not contain the 2 nd dichroic substance O1.
(method for measuring maximum absorption wavelength)
Regarding the absorption spectra of the polarizer 1 (film 1), the films 1-2 and the films 1-4 of example 1, absorbance in the wavelength region of 380 to 800nm was measured at a 1nm pitch, and absorbance (Abs) per 1nm pitch was calculated by the following formula, thereby obtaining an absorption spectrum for each film.
Abs＝Az0/(1+2×S)
From the obtained absorption spectra, the maximum absorption wavelength λ1 of the absorption spectrum of the polarizer 1, the maximum absorption wavelength λ2 of the absorption spectrum of the film 1-2, and the maximum absorption wavelength λ4 of the absorption spectrum of the film 1-4 were obtained. Then, the maximum absorption wavelength λ of the difference spectrum obtained by subtracting the absorption spectrum of the film 1-4 from the absorption spectrum of the polarizer 1 was obtained. The results are shown in table 1.
< maximum absorption wavelength of examples 2 to 31 and comparative examples 1 to 2 >
Films corresponding to examples and comparative examples were produced in the same manner as in example 1, and the maximum absorption wavelength λ1, the maximum absorption wavelength λ2, the maximum absorption wavelength λ4, and the maximum absorption wavelength λ of the difference spectrum were obtained. The results are shown in tables 1 and 2.
< examples 32 to 33, comparative example 3>
The Glass substrate (Central Glass co., ltd. Manufactured, green sheet Glass, 300mm×300mm in size, 1.1mm in thickness) was washed with an alkaline cleaner, and then, after injecting pure water, the Glass substrate was dried.
The following composition for forming an alignment film was applied to the dried glass substrate using a bar #12, and the applied composition for forming an alignment film 2 was dried at 110℃for 2 minutes, thereby forming a coating film on the glass substrate.
The obtained coating film was subjected to rubbing treatment 1 time (rotation speed of roller: 1000 rpm for spacer thickness 2.9mm, stage speed 1.8 m/min) to prepare an alignment film 2 on a glass substrate.
[ chemical formula 30]
From the obtained alignment film 2, a coating film was formed by cutting out the dimensions of 30mm×30mm and spin-coating the polarizer-forming composition 32 (containing the 1 st dichroic material and the 2 nd dichroic material) of table 3 at 800 revolutions.
After the coating film was dried at room temperature for 30 seconds, it was heated at 130℃for 15 seconds.
Next, after cooling the coating film to room temperature, the coating film was heated to 90 ℃ and cooled to room temperature, and polarizer 32 (film 32) was produced.
A film 32-2 was produced in the same manner except that the polarizer-forming composition 32-2 (including the 2 nd dichroic material and not including the 1 st dichroic material) described in table 3 was used instead of the polarizer-forming composition 32.
A film 32-4 was produced in the same manner as above except that the polarizer-forming composition 32-4 (including the 1 st dichroic material and not including the 2 nd dichroic material) described in table 3 was used instead of the polarizer-forming composition 32.
A laminate having the polarizer 33 of example 33, films 33-2 and 33-4 corresponding to the polarizer 33 (film 33), a laminate having the polarizer 3B (film 3B) of comparative example 3, and films 3B-2 and 3B-4 corresponding to the polarizer 3B were produced in the same order as in example 32, except that the compositions for forming polarizers described in table 3 were used.
Then, the maximum absorption wavelength λ1, the maximum absorption wavelength λ2, the maximum absorption wavelength λ4, and the maximum absorption wavelength λ of the difference spectrum are obtained. The results are shown in table 3.
[ chemical formula 31]
[ XRD Spectrum ]
< XRD Spectrum of example 1 >
When XRD spectra were measured in example 1, films 1-2 and films 1-3 were produced. The method for producing the film 1-2 is described in the measurement of the maximum absorption wavelength.
(films 1-3)
The films 1 to 3 are films produced in the same manner as the polarizer 1 except that the following polarizer-forming composition 1 to 3 is used, and do not contain the 1 st dichroic substance M1 and the 2 nd dichroic substance O1.
(method for measuring XRD Spectrometry)
XRD spectra of polarizer 1, films 1-2 and films 1-3 of example 1 were measured. The obtained film (polarizer) was cut into a size of 40mm×40mm, and X-ray was irradiated onto the surface of the polarizer by using an X-ray diffraction apparatus for thin film evaluation (manufactured by Riga ku Corporation, trade name: smartLab) under the following conditions to perform in-plane XRD.
Using a Cu radiation source (CuK alpha, output 45kV, 200 mA)
Incident angle of X-ray 0.2 DEG
Using an optical system: parallel optical System (CBO (Cross Beam Optics: cross Beam optical System) (PB (Parallel Beam))
0.2mm Inlet side Inlet slit 0.5 degree PSC (Parallel Slit Collimator: parallel slit collimator) in parallel slit plane, 10mm long side limiting slit
Light receiving slit 20mm on light receiving side, PSA (Parallel Slit Analyzer: parallel slit analyzer) 0.5 degree in light receiving parallel slit plane
Scanning sweepConditions are described: the range of 1 to 40 degrees is set to 0.008 degrees/step, 2.0 degrees/min (mi)
Scanning conditions: setting the range of-120 degree to 0.5 degree/step and 9.6 degree/min
The direction in which the polymer liquid crystal and the dichroic material are aligned in the long axis direction is defined as azimuth angleIn-plane measurement of all directions (++) was performed on a 15 degree scale>Scanning) by performing +.>Scanning determines the direction in the plane of the substrate where the peak intensity is high. Both assays were performed using cukα at an angle of incidence of 0.20 °. The period length was obtained from the relationship between the diffraction angle and the distance described below using the peak obtained from the measurement of the orientation direction (direction determined as described above). The film thickness was normalized to be the X-ray incidence length at an X-ray incidence angle of 0.2 °, and the peak intensity (cps expression) was calculated.
d=λ/(2×sin θ) (d: distance, λ: incident X-ray wavelength (cukα;))
in the films 1 to 3, in the 0 ° direction (the direction determined as described above), the film was stretched at 2θ of 2.8 ° (period length:) 4.9 ° (cycle length: />) 7.9 ° (cycle length: />) A peak was observed at the position (refer to fig. 5). In contrast, in film 1-2, the film was oriented at 2.8℃except in the 0℃direction (direction determined as described above) (period length:. About.>) 4.9 ° (cycle length: />)、7.9°
(cycle length:) A peak was observed at the position of (a) and at 6.0 ° (period length: />) A peak was observed at the position (refer to fig. 4). Thus, it was found that the peak at 6.0 ° was a peak derived from the 2 nd dichroic material O1. The peak intensity of this peak was 530.
In contrast, in the polarizer 1, at 2.8 ° (period length:) 4.9 ° (cycle length: />) 7.9 ° (cycle length: />) The peak (refer to fig. 6) was observed at the position of (a) and the peak of 6.0 ° observed in the film 1-2 was not observed.
As a result, in the polarizer 1, since the 1 st dichroic material and the 2 nd dichroic material have an arrangement structure (specifically, a crystal structure), it is assumed that the peak of the 2 nd dichroic material O1 disappears.
XRD spectra of examples 2 to 31 and comparative examples 1 to 2
In the same manner as in example 1, films corresponding to each example and comparative example were produced, and the state of the peak derived from the 2 nd dichroic material O in the polarizer was observed.
As a result, in the polarizers of examples 2 to 31, the peak derived from the 2 nd dichroic substance O disappeared or was smaller than the peak intensity derived from the 2 nd dichroic substance O in the film corresponding thereto (i.e., the film containing no 1 st dichroic substance M but containing the 2 nd dichroic substance O). Accordingly, it is assumed that the polarizers of examples 2 to 31 have an arrangement structure (specifically, a crystal structure) of the 1 st dichroic material and the 2 nd dichroic material.
In contrast, the peak intensities of the polarizers of comparative examples 1 and 2 derived from the 2 nd dichroic material O were equal to the peak intensities of the corresponding films (i.e., the films containing no 1 st dichroic material M but no 2 nd dichroic material O) derived from the 2 nd dichroic material O. Accordingly, in the polarizer of the comparative example, it is assumed that the 1 st dichroic material and the 2 nd dichroic material have no aligned structure.
Next, a film 2-4 was produced in the same manner as in the polarizer 1, except that the following polarizer-forming composition 2-4 was used. Films 2-4 contain the 1 st dichroic substance M1 but do not contain the 2 nd dichroic substance O1.
In-plane measurement of all directions was performed on the obtained films 2, 2-3 and 2-4 in the same manner on a scale of 15 DEG [ ]Scanning) by performing +.>Scanning to determine the direction in the plane of the substrate where the peak intensity is high.
In the direction of 57 ° (the direction determined as described above), no peak was observed at 2θ of 17 ° or less in films 2 to 4 (films containing the 1 st dichroic substance but not containing the 2 nd dichroic substance), films 2 to 2 (films containing no 1 st dichroic substance but not containing the 2 nd dichroic substance), and films 2 to 3 (films containing no 1 st dichroic substance and no 2 nd dichroic substance) (refer to fig. 7, 8, and 9).
In contrast, in the film 2 (film containing the 1 st dichroic material and the 2 nd dichroic material), the ratio of 2θ was 3.1 ° (period length:) A peak was observed at the position of (refer to fig. 10). The peak intensity of this peak was 560.
This can determine that 2θ is 3.1 ° (cycle length:) The peaks at the positions of (a) are peaks of crystal structures of the 1 st dichroic substance and the 2 nd dichroic substance. Thus, from this point of view, it is also assumed that the 1 st dichroic material and the 2 nd dichroic material form an aligned structure (specifically, a crystal structure) in the film 2.
[ stabilization energy ]
The polarizers of examples 1, 4 to 7, 12 to 15, 20 to 31 and comparative example 1 were calculated using the AMBER11 according to the above calculation method, and the stabilization energy (unit kcal/mol) and the stabilization energy ratio were calculated. The smaller the stabilization energy, the easier the arrangement structure of the 1 st dichroic substance and the 2 nd dichroic substance is formed. The calculation results of the stabilization energy and the stabilization energy ratio are shown in table 4.
In the above calculation method, the 1 st dichroic substance corresponds to the dichroic substance a, and the 2 nd dichroic substance corresponds to the dichroic substance B.
/>
/>
TABLE 4
Stabilization energy (kcal/mol) Stabilization energy ratio
Example 1 14.8 0.84
Example 4 34.4 0.62
Example 5 28.1 0.69
Example 6 21.8 0.76
Example 7 14.8 0.84
Example 12 15.9 0.83
Example 13 15.6 0.83
Example 14 16.5 0.82
Example 15 16.8 0.82
Example 20 34.2 0.62
Example 21 18.8 0.79
Example 22 42.5 0.52
Example 23 40.5 0.54
Example 24 36.6 0.59
Example 25 5.9 0.92
Example 26 -8.2 1.19
Example 27 -11.3 1.03
Example 28 13.4 0.73
Example 29 -3.1 1.25
Example 30 58.6 0.34
Example 31 43.5 0.43
Comparative example 1 72.4 0.21
The log p difference in tables 1 and 2 means a difference between the log p values of the group corresponding to R1 in the formula (1) and the group corresponding to R4 in the formula (2) in the case where the 1 st dichroic substance M has the structure represented by the formula (1) and the 2 nd dichroic substance O has the structure represented by the formula (2).
From the measurement results of the maximum absorption wavelength, it is assumed that the 1 st dichroic substance and the 2 nd dichroic substance form an association in the polarizer of the example. Further, from the measurement results of XRD spectrum, it is assumed that the 1 st dichroic substance and the 2 nd dichroic substance form crystal structures in the polarizer of the example. Thus, it can be said that the 1 st dichroic substance and the 2 nd dichroic substance form an aligned structure in the polarizer of the embodiment. As described above, the polarizers according to examples in which the 1 st dichroic material and the 2 nd dichroic material were formed with an arrangement structure, as shown in the evaluation results of table 1, exhibited a high degree of orientation compared to the polarizers of comparative examples.
Symbol description
P-polarizer, M- (1 st dichroic substance) molecule, O- (2 nd dichroic substance) molecule, L- (liquid crystalline compound) molecule, G-aggregate, w-width, a-angle.

Claims (14)

1. A polarizer is formed from a composition for forming a polarizer, which contains a liquid crystalline compound, a 1 st dichroic substance, and a 2 nd dichroic substance,
the 1 st dichroic substance is a compound represented by the formula (1),
the 2 nd dichroic substance is a compound represented by the formula (2),
The polarizer has an arrangement structure formed of the 1 st dichroic substance and the 2 nd dichroic substance,
the stabilization energy indicating the energy loss upon entering one of the 1 st dichroic substance and the 2 nd dichroic substance in the structure in which the other dichroic substance is arranged alone is less than 72kcal/mol,
the structure in which one kind of dichroic substance is arranged alone is a structure in which only one kind of dichroic substance is arranged,
in the formula (1), ar1 and Ar2 each independently represent a phenylene group which may have a substituent, or a naphthylene group which may have a substituent,
r1 represents a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, an alkoxy group, an alkylthio group, an alkylsulfonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an acyloxy group, an alkylcarbonate group, an alkylamino group, an amido group, an alkylcarbonylamino group, an alkoxycarbonylamino group, an alkylsulfonylamino group, an alkylsulfamoyl group, an alkylcarbamoyl group, an alkylsulfinyl group, an alkylureyl group, an alkylphosphoramido group, an alkylimino group or an alkylsilyl group,
r2 and R3 each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, an alkenyl group, an alkoxy group, an acyl group, an alkoxycarbonyl group, an alkylamido group, an alkylsulfonyl group, an aryl group, an arylcarbonyl group, an arylsulfonyl group, an aryloxycarbonyl group or an aralkyloxy group,
In formula (2), n represents 1 or 2,
ar3 and Ar4 each independently represent a phenylene group which may have a substituent,
ar5 represents a phenylene group which may have a substituent, a naphthylene group which may have a substituent or a heterocyclic group which may have a substituent,
r4 represents a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, an alkoxy group, an alkylthio group, an alkylsulfonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an acyloxy group, an alkylcarbonate group, an alkylamino group, an amido group, an alkylcarbonylamino group, an alkoxycarbonylamino group, an alkylsulfonylamino group, an alkylsulfamoyl group, an alkylcarbamoyl group, an alkylsulfinyl group, an alkylureyl group, an alkylphosphoramido group, an alkylimino group or an alkylsilyl group,
r5 and R6 each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, an alkenyl group, an alkoxy group, an acyl group, an alkoxycarbonyl group, an alkylamido group, an alkylsulfonyl group, an aryl group, an arylcarbonyl group, an arylsulfonyl group, an aryloxycarbonyl group or an aralkyloxy group,
wherein, when R4 represents an alkyl group, the carbon atom of the alkyl group in R4 may be replaced by-O-, -CO-, -C (O) -O-, -O-C (O) -, -Si (CH) 3 ) 2 -O-Si(CH 3 ) 2 -N (R1 '), -CO-N (R1'), -C (O) -O-, -O-C (O) -N (R1 '), -N (R1') -C (O) -N (R1 '), -ch=ch-, -c≡c-, -n=n-, -C (R1')=ch-C (O) -or-O-C (O) -O-substituted, R1 'represents a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms, and when a plurality of R1's are present in each group, they may be the same as each other or different from each other.
2. The polarizer of claim 1, wherein,
the absolute value of the difference between the maximum absorption wavelength lambda 2 and the maximum absorption wavelength lambda is greater than 2nm,
the maximum absorption wavelength lambda 2 is the maximum absorption wavelength in the absorption spectrum of a film formed from a composition containing the 2 nd dichroic substance and the liquid crystalline compound without containing the 1 st dichroic substance,
the maximum absorption wavelength λ is the maximum absorption wavelength in the difference spectrum between the absorption spectrum of the polarizer and the absorption spectrum of a film formed of a composition containing the 1 st dichroic substance and the liquid crystalline compound without the 2 nd dichroic substance.
3. The polarizer according to claim 1 or 2, wherein,
the absolute value of the difference between the maximum absorption wavelength lambda 4 and the maximum absorption wavelength lambda 1 is greater than 2nm,
The maximum absorption wavelength lambda 4 is the maximum absorption wavelength in the absorption spectrum of a film formed from a composition containing the 1 st dichroic substance and the liquid crystalline compound without containing the 2 nd dichroic substance,
the maximum absorption wavelength λ1 is the maximum absorption wavelength in the absorption spectrum of the polarizer.
4. The polarizer according to claim 1 or 2, wherein,
the intensity of the peak O1 is different from the intensity of the peak O2,
the peak O1 is a peak derived from the periodic structure of the 2 nd dichroic substance in the X-ray diffraction spectrum of the polarizer,
the peak O2 is a peak derived from the periodic structure of the 2 nd dichroic substance in an X-ray diffraction spectrum of a film formed of a composition containing the 2 nd dichroic substance and the liquid crystalline compound without containing the 1 st dichroic substance.
5. The polarizer of claim 4, wherein,
the ratio of the intensity of the peak O1 to the intensity of the peak O2 is less than 1.
6. The polarizer according to claim 1 or 2, wherein,
in case of measuring the X-ray diffraction spectrum of the polarizer,
the peak OM originating from the periodic structures of the 1 st dichroic substance and the 2 nd dichroic substance is detected at a diffraction angle different from a diffraction angle of a peak M2 originating from the periodic structures of the 1 st dichroic substance in an X-ray diffraction spectrum in which a film formed of a composition containing no 2 nd dichroic substance and the liquid crystal compound is detected, and a diffraction angle of a peak O2 originating from the periodic structures of the 2 nd dichroic substance in an X-ray diffraction spectrum in which a film formed of a composition containing no 1 st dichroic substance and the liquid crystal compound is detected.
7. The polarizer according to claim 1 or 2, wherein,
the stabilization energy is 55kcal/mol or less.
8. The polarizer according to claim 1 or 2, wherein,
the stabilization energy is 35kcal/mol or less.
9. The polarizer according to claim 1 or 2, wherein,
the 1 st dichroic substance is a dichroic substance having a maximum absorption wavelength in a range of 560nm or more and 700nm or less,
the 2 nd dichroic substance is a dichroic substance having a maximum absorption wavelength in a range of 455nm or more and less than 560 nm.
10. The polarizer according to claim 1 or 2, wherein,
the absolute value of the difference between the log p value of R1 in the formula (1) and the log p value of R4 in the formula (2) is 2.30 or less.
11. The polarizer according to claim 1 or 2, further comprising a 3 rd dichroic substance having a maximum absorption wavelength in a range of 380nm or more and less than 455 nm.
12. A polarizer is formed from a composition for forming a polarizer, which contains a liquid crystalline compound and a dichroic substance comprising a 1 st dichroic substance and a 2 nd dichroic substance,
the polarizer having a crystal structure formed of the 1 st dichroic substance and the 2 nd dichroic substance,
The stabilization energy indicating the energy loss upon entering one of the 1 st dichroic substance and the 2 nd dichroic substance in the structure in which the other dichroic substance is arranged alone is less than 72kcal/mol,
the structure in which one kind of dichroic substance is arranged alone is a structure in which only one kind of dichroic substance is arranged.
13. The polarizer according to claim 12, wherein the content of the dichroic substance is 12.9 to 99 parts by mass based on 100 parts by mass of the total amount of the dichroic substance and the liquid crystalline compound.
14. An image display device having the polarizer of any one of claims 1 to 13.
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